JP2015136849A - Resin substrate, metal-clad laminate, printed wiring board, and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin substrate for forming a printed wiring board excellent in fine wiring line processability.SOLUTION: A resin substrate 100 includes a fiber base material layer 101 comprising a fiber base material and a resin layer 103 containing no fiber base material and disposed on one surface or both surfaces of the fiber base material layer 101. The resin layer 103 comprises an epoxy resin (A) and an inorganic filler (B), in which an average particle diameter of an inorganic filler (B1) in a surface part A1 in a thickness direction of the resin layer 103, obtained by an observation image by a scanning electron microscope, is larger than an average particle diameter of an inorganic filler (B2) present on an interface A2 between the resin layer 103 and the fiber base material layer 101.

Description

  The present invention relates to a resin substrate, a metal-clad laminate, a printed wiring board, and a semiconductor device.

In recent years, along with the demand for higher functionality of electronic devices, higher density integration of electronic components and further higher density mounting have progressed, and printed wiring boards used for these are smaller and thinner than before. , Higher density, and multi-layering are progressing. Accordingly, there is a need for a printed wiring board that can be thinned and that can form high-density and fine circuits.
As a method for forming a fine circuit, an SAP (semi-additive process) method has been proposed. In the SAP method, first, a roughening treatment is performed on the surface of the insulating layer, and an electroless metal plating film serving as a base is formed on the surface of the insulating layer. Next, the non-circuit forming portion is protected by the plating resist, and the copper thickness of the circuit forming portion is thickened by electrolytic plating. Thereafter, the plating resist is removed, and the electroless metal plating film other than the circuit forming portion is removed by flash etching, thereby forming a circuit on the insulating layer. In the SAP method, since the metal layer laminated on the insulating layer can be thinned, finer circuit wiring is possible.

  On the other hand, when the semiconductor package is miniaturized, the thickness of the semiconductor element and the sealing material, which conventionally has been responsible for most of the rigidity of the semiconductor package, becomes extremely thin, and the semiconductor package is likely to warp. In addition, since the proportion of the printed wiring board as a component increases, the physical properties and behavior of the printed wiring board have a great influence on the warpage of the semiconductor package.

  In general, the difference in thermal expansion between a semiconductor element and a printed wiring board on which the semiconductor element is mounted is large. For this reason, when exposed to high temperatures, the semiconductor package may be greatly warped due to thermal stress caused by a difference in thermal expansion.

As a technique for suppressing such warpage of the semiconductor package, for example, a technique described in Patent Document 1 below can be cited.
Patent Document 1 describes a prepreg and a laminate using a thermosetting resin composition containing a curing agent having an N-substituted maleimide group and an acidic substituent, and a bisphenol F-type phenol novolac-type epoxy resin. .

JP2012-21098A

  However, conventional insulating layers have poor electroless plating properties and are inferior in fine wiring processability.

  This invention is made | formed in view of the said situation, and provides the resin substrate for printed wiring board formation which is excellent in fine wiring workability.

  As a result of intensive studies, the present inventors have found that the fine wiring processability of the resin substrate is improved by relatively increasing the average particle diameter of the inorganic filler in the surface portion in the thickness direction of the resin layer. .

  The present invention has been invented based on such knowledge.

That is, according to the present invention,
A fiber substrate layer including a fiber substrate;
A resin layer provided on one or both sides of the fiber substrate layer, and not including the fiber substrate;
A resin substrate for forming a printed wiring board comprising:
The resin layer contains an epoxy resin and an inorganic filler,
The average particle diameter of the inorganic filler at the surface portion in the thickness direction of the resin layer, which is obtained from the observation image of the scanning electron microscope, is the average of the inorganic filler at the boundary between the resin layer and the fiber base layer. A resin substrate larger than the particle diameter is provided.

  Furthermore, according to the present invention, there is provided a metal-clad laminate in which a metal foil is provided on one or both sides of the resin substrate or a laminate in which two or more resin substrates are stacked.

  Furthermore, according to this invention, the printed wiring board by which the circuit layer is provided in the single side | surface or both surfaces of the said resin substrate is provided.

  Furthermore, according to the present invention, there is provided a semiconductor device in which a semiconductor element is mounted on the circuit layer of the printed wiring board.

  ADVANTAGE OF THE INVENTION According to this invention, the resin substrate for printed wiring board formation which is excellent in fine wiring processability can be provided.

It is sectional drawing which shows an example of a structure of the resin substrate in this embodiment. It is sectional drawing which shows an example of a structure of the resin substrate in this embodiment. It is sectional drawing which shows an example of a structure of the metal-clad laminated board in this embodiment. It is sectional drawing which shows an example of the manufacturing method of the prepreg in this embodiment. It is sectional drawing which shows an example of a structure of the printed wiring board in this embodiment. It is sectional drawing which shows an example of a structure of the printed wiring board in this embodiment. It is sectional drawing which shows an example of a structure of the semiconductor device in this embodiment. It is sectional drawing which shows an example of a structure of the semiconductor device in this embodiment.

  Embodiments of the present invention will be described below with reference to the drawings. In all the drawings, similar constituent elements are denoted by common reference numerals, and description thereof is omitted as appropriate. Moreover, the figure is a schematic diagram and does not necessarily match the actual dimensional ratio.

First, the structure of the resin substrate in this embodiment is demonstrated. 1 and 2 are cross-sectional views illustrating an example of the configuration of the resin substrate 100 according to the present embodiment.
The resin substrate 100 includes a fiber base layer 101 including a fiber base, and a resin layer 103 provided on one or both sides of the fiber base layer 101 and not including the fiber base.
The resin layer 103 contains an epoxy resin (A) and an inorganic filler (B), and the inorganic filler (B1) on the surface portion A1 in the thickness direction of the resin layer 103, which is obtained from an observation image of a scanning electron microscope. ) Is larger than the average particle diameter of the inorganic filler (B2) at the boundary portion A2 between the resin layer 103 and the fiber base layer 101.
The resin substrate 100 is a resin substrate for forming a printed wiring board, and is used for forming an insulating layer of the printed wiring board.

  The average particle diameters of the inorganic fillers (B1) and (B2) can be measured by image analysis of electron micrographs. For example, the measurement is performed according to the following procedure. First, a cross section of the resin substrate 100 is photographed with a scanning electron microscope. From the observed image, 100 inorganic fillers (B) are arbitrarily selected, and their particle diameters are approximated by a circle and measured. The average particle diameter can be obtained by integrating all the particle diameters and dividing by the number.

According to the inventor's study, by increasing the rigidity of the resin substrate, it is possible to reduce the warpage of the resulting semiconductor package, while reducing the fine wiring processability, or the insulation reliability of the obtained printed wiring substrate. It became clear that sex fell.
As a result of intensive studies in view of the above circumstances, the present inventor has improved the fine wiring processability of the resin substrate by relatively increasing the average particle diameter of the inorganic filler on the surface portion in the thickness direction of the resin layer. I found. This is because when the average particle diameter of the inorganic filler on the surface portion in the thickness direction of the resin layer is relatively large, when the surface of the resin substrate is roughened, it has excellent adhesion to the metal layer (circuit layer). This is probably because the surface of the resin layer can be formed.

  In the resin substrate 100, an inorganic filler having a relatively large average particle diameter is present on the surface portion in the thickness direction of the resin layer. Thereby, the adhesiveness of a circuit layer and a resin substrate improves, As a result, the fine wiring processability and the insulation reliability of a printed wiring board can be improved.

  In order to adjust the average particle diameter of the inorganic filler (B) in the thickness direction of the resin layer 103, as described later, the inorganic filler (B) contained in the epoxy resin compositions (A) and (B) It is important to select an appropriate type and set its content appropriately.

The average particle diameter of the inorganic filler (B1) in the thickness direction surface portion A1 of the resin layer 103 is preferably 0.04 μm or more and 5.0 μm or less, more preferably 0.2 μm or more and 3.0 μm or less, Preferably they are 1.0 micrometer or more and 2.5 micrometers or less.
The average particle diameter of the inorganic filler (B2) at the boundary portion A2 between the resin layer 103 and the fiber base layer 101 is preferably 0.04 μm or more and less than 5.0 μm, more preferably 0.1 μm or more and 1.3 μm. It is below, More preferably, they are 0.2 micrometer or more and 0.8 micrometer or less.

Further, the resin substrate 100, the inorganic filler in the boundary portion A2 of the fibrous substrate layer 101 of the resin layer 103 a content of (B2) and FC _1, the inorganic filler in the thickness direction surface portions A1 of the resin layer 103 ( when the content of B1) was FC _2, preferably satisfy the relation of FC 1> FC _2. Thereby, in the thickness direction surface portion A1, the adhesion between the circuit layer and the resin substrate can be further improved, and the rigidity of the resin substrate 100 can be increased. As a result, the warpage of the obtained semiconductor package can be further reduced, and the fine wiring processability and the insulation reliability of the printed wiring board can be further improved.

The content (FC ₁ ) of the inorganic filler (B2) is preferably 50% by mass to 90% by mass, and more preferably 55% by mass to 80% by mass.
Here, the content (FC ₁ ) of the inorganic filler (B2) is a resin layer obtained by cutting out a region from the boundary between the resin layer 103 and the fiber base layer 101 to 5 μm toward the surface of the resin substrate 100. Can be measured from In addition, let the weight of the cut-out resin layer be 100 mass%.
In addition, the content (FC ₂ ) of the inorganic filler (B1) is preferably 20% by mass or more and 60% by mass or less, and more preferably 25% by mass or more and 55% by mass or less.
Here, the content (FC ₂ ) of the inorganic filler (B1) can be measured from the resin layer cut out from the surface of the resin substrate 100 in the thickness direction up to 5 μm. In addition, let the weight of the cut-out resin layer be 100 mass%.

As shown in FIG. 2, the resin layer 103 is provided on the opposite side of the first resin layer 103 a in contact with the fiber base layer 101 and the fiber base layer 101 of the first resin layer 103 a, and on the resin substrate 100. And a second resin layer 103b constituting the thickness direction surface portion. Thereby, the content rate and the average particle diameter of the inorganic filler (B1) in the thickness direction surface portion A1 and the content rate and the average of the inorganic filler (B2) in the boundary portion A2 between the fiber base layer 101 of the resin layer 103. The resin substrate 100 having a different particle diameter can be obtained.
For example, the 1st resin layer 103a consists of an epoxy resin composition (A) mentioned later, and the 2nd resin layer 103b consists of a different kind of epoxy resin composition (B) from an epoxy resin composition (A).

  The thickness of the 1st resin layer 103a becomes like this. Preferably they are 5 micrometers or more and 100 micrometers or less, More preferably, they are 7.5 micrometers or more and 25 micrometers or less. The thickness of the second resin layer 103b is preferably 0.5 μm or more and 25 μm or less, and more preferably 1 μm or more and 15 μm or less.

  The resin layer 103 preferably does not include a clear layer interface from the viewpoint of improving the adhesion between the first resin layer 103a and the second resin layer 103b.

In order to more effectively obtain the effect of preventing warpage of the resin substrate 100, the glass transition temperature of the resin substrate 100 by dynamic viscoelasticity measurement is preferably 170 ° C. or higher, more preferably 180 ° C. or higher. Yes, more preferably 190 ° C or higher. About an upper limit, 350 degrees C or less is preferable, for example.
When the glass transition temperature by the dynamic viscoelasticity measurement satisfies the above range, the resin substrate 100 increases the rigidity of the resin substrate 100 and can further reduce the warp of the resin substrate 100 during mounting. As a result, the semiconductor device obtained from the resin substrate 100 can further suppress the positional deviation of the semiconductor element with respect to the printed wiring board, and can further improve the connection reliability between the semiconductor element and the printed wiring board.

Moreover, in order to obtain the effect of preventing warpage of the resin substrate 100 more effectively, the storage elastic modulus E ′ at 250 ° C. of the resin substrate 100 is preferably 0.1 GPa or more, although not particularly limited. Preferably it is 0.5 GPa or more. Although it does not specifically limit about an upper limit, For example, it can be 20 GPa or less.
When the storage elastic modulus E ′ at 250 ° C. satisfies the above range, the resin substrate 100 increases the rigidity of the resin substrate 100 and can further reduce the warp of the resin substrate 100 during mounting. As a result, the semiconductor device obtained from the resin substrate 100 can further suppress the positional deviation of the semiconductor element with respect to the printed wiring board, and can further improve the connection reliability between the semiconductor element and the printed wiring board.

  The thickness of the resin substrate 100 is, for example, 10 μm or more and 500 μm or less. When the thickness of the resin substrate 100 is within the above range, the balance of mechanical strength and productivity is particularly excellent, and the resin substrate 100 suitable for a thin printed wiring board can be obtained.

  FIG. 3 is a cross-sectional view showing an example of the configuration of the metal-clad laminate 200 in the present embodiment. The metal-clad plate 200 is provided with a metal foil 105 on one side or both sides of a resin substrate 100 (insulating layer 301) or a laminate (insulating layer 301) in which two or more resin substrates 100 are stacked. The metal-clad laminate 200 can be used for forming an insulating layer of a printed wiring board.

  Next, a method for manufacturing the resin substrate 100 will be described. The resin substrate 100 is obtained by heat-curing the prepreg (P).

Here, the manufacturing method of a prepreg (P) is demonstrated.
First, the resin layer which consists of an epoxy resin composition (A) is laminated on a fiber base material, and sheet-like prepreg (P1) is obtained by making it harden | cure after that. Next, a resin layer made of a different type of epoxy resin composition (B) from the epoxy resin composition (A) is laminated on the obtained prepreg (P1), and then semi-cured. By doing so, the prepreg (P) can be obtained. Moreover, in this embodiment, the layer containing a fiber base material is the fiber base material layer 101 among the layers formed by curing the prepreg (P), and the other layer not containing the fiber base material is the resin layer 103. is there.

  In the present embodiment, the fiber base material is impregnated with the resin layer made of the epoxy resin composition (A) by laminating the fiber base material with the resin layer with the supporting base material from both sides of the fiber base material. In addition, when laminating the resin layer with a supporting substrate, it is preferable to use a vacuum laminating apparatus or the like.

  The manufacturing process of the prepreg (P1) using the method of laminating a fiber base material with the resin layer with a support base material from both surfaces of a fiber base material is demonstrated using FIG.

  First, carrier materials 5a and 5b and a fiber base material 11 are prepared as materials. Further, a vacuum laminating device 60 and a hot air drying device 62 are prepared as devices. Carrier material 5a, 5b is comprised by the resin layer (A) which consists of an epoxy resin composition (A). The carrier materials 5a and 5b can be obtained, for example, by a method of applying a resin varnish of the epoxy resin composition (A) to a carrier film.

  Next, a bonded body is formed by bonding the carrier material 5a, the fiber base material 11, and the carrier material 5b in this order using the vacuum laminating apparatus 60. The vacuum laminating apparatus 60 includes a roll that winds up the carrier material 5a, a roll that winds up the carrier material 5b, a roll that winds up the fiber substrate 11, and a laminating roll 61. Under reduced pressure, the carrier material 5a and the carrier material 5b fed from each roll are superposed on both surfaces of the fiber base material 11. Then, for example, the stacked laminates are joined by the laminate roll 61 in a vacuum at a temperature of 60 ° C. or higher and 150 ° C. or lower. Thereby, the joined body comprised from the carrier material 5a, the fiber base material 11, and the carrier material 5b is obtained.

  In such a joining process, other devices such as a vacuum box device and a vacuum becquerel device can be used, for example.

  Next, heat treatment is performed using a hot air drying device 62 at a temperature equal to or higher than the melting temperature of the epoxy resin composition constituting each of the carrier materials 5a and 5b constituting the joined body. Other methods of heat treatment can be carried out using, for example, an infrared heating device, a heating roll device, a flat platen hot platen press device, or the like.

  After laminating the carrier materials 5a and 5b to the fiber substrate 11, the carrier film is peeled off. By this method, the epoxy resin composition (A) is supported on the fiber base material 11, and a prepreg (P1) including the epoxy resin composition (A) and the fiber base material 11 is obtained.

  It continues and demonstrates the manufacturing method of the prepreg (P) using the prepreg (P1) obtained above.

  First, a resin layer (B) made of an epoxy resin composition (B) is prepared as a material. The resin layer (B) can be obtained, for example, by a method of applying a resin varnish of the epoxy resin composition (B) to a carrier film.

  Next, a bonded body in which the resin layer (B), the prepreg (P1), and the resin layer (B) are bonded in this order is formed using a vacuum laminator. By this method, the resin layer (B) which consists of an epoxy resin composition (B) is formed in both surfaces of a prepreg (P1), and a prepreg (P) can be obtained.

Next, a method for manufacturing the metal-clad laminate 200 and the resin substrate 100 using the prepreg (P) obtained above will be described. A method for manufacturing the metal-clad laminate 200 and the resin substrate 100 using the prepreg (P) is, for example, as follows.
Prepreg (P) or two or more prepregs (P) are laminated on the upper and lower surfaces or one side of the laminated body, and the metal foil 105 is stacked on top of each other, and these are joined under high vacuum conditions using a laminator device or a becquerel device. Alternatively, the metal foil 105 is overlapped on the upper and lower surfaces or one surface outside the prepreg (P) as it is. When two or more prepregs (P) are laminated, the metal foil 105 is placed on the outermost upper and lower surfaces or one surface of the laminated prepreg (P).
Subsequently, the metal-clad laminate 200 can be obtained by heat-pressing the laminate in which the prepreg (P) and the metal foil 105 are stacked. Here, it is preferable to continue the pressurization until the end of cooling at the time of heat-pressure molding.

The heating temperature at the time of the above-described heating and pressing is preferably 120 ° C. or higher and 250 ° C. or lower, and more preferably 150 ° C. or higher and 240 ° C. or lower.
Moreover, the pressure at the time of the above-described heat and pressure molding is preferably 0.5 MPa or more and 5 MPa or less, and more preferably a high pressure of 2.5 MPa or more and 5 MPa or less.

  Further, after the heat and pressure molding, if necessary, post-curing may be performed in a thermostatic bath or the like. The post-curing temperature is preferably 150 ° C. or higher and 300 ° C. or lower, more preferably 250 ° C. or higher and 300 ° C. or lower.

  The resin substrate 100 can be obtained by removing the metal foil 105 from the metal-clad laminate 200.

  Moreover, a printed wiring board can be obtained using the metal-clad laminate 200 or the resin substrate 100 as a core substrate.

  Hereinafter, each material used when manufacturing the metal-clad laminate 200 and the resin substrate 100 will be described in detail.

Examples of the metal constituting the metal foil 105 include copper and copper alloys, aluminum and aluminum alloys, silver and silver alloys, gold and gold alloys, zinc and zinc alloys, nickel and nickel alloys, tin and Examples thereof include tin alloys, iron and iron alloys, Kovar (trade name), 42 alloys, Fe-Ni alloys such as Invar and Super Invar, W or Mo, and the like. Among these, the metal constituting the metal foil 105 is preferably copper or a copper alloy because of its excellent conductivity, easy circuit formation by etching, and low cost. That is, the metal foil 105 is preferably a copper foil.
Further, as the metal foil 105, a metal foil with a carrier or the like can also be used.
The thickness of the metal foil 105 is preferably 0.5 μm or more and 20 μm or less, and more preferably 1.5 μm or more and 18 μm or less.

  Epoxy resin compositions (A) and (B) contain an epoxy resin (A) and an inorganic filler (B), respectively.

  Examples of the epoxy resin (A) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, bisphenol M type epoxy resin (4,4 ′-(1,3- Phenylenediisopridiene) bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4 '-(1,4-phenylenediisopridiene) bisphenol type epoxy resin), bisphenol Z type epoxy resin (4,4' -Cyclohexidiene bisphenol type epoxy resin), etc .; phenol novolac type epoxy resin, cresol novolac type epoxy resin, tetraphenol group ethane type novolac type epoxy resin, condensed ring aromatic hydrocarbon structure Novolak-type epoxy resins such as volac-type epoxy resins; biphenyl-type epoxy resins; aralkyl-type epoxy resins such as xylylene-type epoxy resins and biphenyl-aralkyl-type epoxy resins; naphthylene ether-type epoxy resins, naphthol-type epoxy resins, naphthalenediol-type epoxy resins Naphthalene type epoxy resins such as bifunctional to tetrafunctional epoxy type naphthalene resins, binaphthyl type epoxy resins, naphthalene aralkyl type epoxy resins; anthracene type epoxy resins; phenoxy type epoxy resins; dicyclopentadiene type epoxy resins; norbornene type epoxy resins; Examples thereof include adamantane type epoxy resins and fluorene type epoxy resins.

  As the epoxy resin (A), one of these may be used alone, two or more may be used in combination, and one or two or more thereof and a prepolymer thereof may be used in combination. .

  Among epoxy resins (A), bisphenol type epoxy resin, novolac type epoxy resin, biphenyl type epoxy resin, aralkyl type epoxy resin, naphthalene type from the viewpoint of further improving the heat resistance and insulation reliability of the obtained printed wiring board One or more selected from the group consisting of epoxy resins, anthracene type epoxy resins and dicyclopentadiene type epoxy resins are preferred, aralkyl type epoxy resins, novolak type epoxy resins having a condensed ring aromatic hydrocarbon structure and naphthalene types One or more selected from the group consisting of epoxy resins are more preferred.

  As the bisphenol A type epoxy resin, “Epicoat 828EL” and “YL980” manufactured by Mitsubishi Chemical Corporation can be used. As the bisphenol F type epoxy resin, “jER806H” and “YL983U” manufactured by Mitsubishi Chemical Corporation, “EPICLON 830S” manufactured by DIC Corporation, and the like can be used. As the bifunctional naphthalene type epoxy resin, “HP4032”, “HP4032D”, “HP4032SS” manufactured by DIC, and the like can be used. As the tetrafunctional naphthalene type epoxy resin, “HP4700” and “HP4710” manufactured by DIC, etc. can be used. As the naphthol type epoxy resin, “ESN-475V” manufactured by Nippon Steel Chemical Co., Ltd., “NC7000L” manufactured by Nippon Kayaku Co., Ltd. and the like can be used. As the aralkyl type epoxy resin, “NC3000”, “NC3000H”, “NC3000L”, “NC3000S”, “NC3000S-H”, “NC3100” manufactured by Nippon Kayaku Co., Ltd., “ESN-170” manufactured by Nippon Steel Chemical Co., Ltd. And “ESN-480” can be used. As the biphenyl type epoxy resin, “YX4000”, “YX4000H”, “YX4000HK”, “YL6121” and the like manufactured by Mitsubishi Chemical Corporation can be used. As the anthracene type epoxy resin, “YX8800” manufactured by Mitsubishi Chemical Corporation can be used. As the naphthylene ether type epoxy resin, “HP6000”, “EXA-7310”, “EXA-7311”, “EXA-7311L”, “EXA7311-G3” and the like manufactured by DIC can be used.

  As the epoxy resin (A), one of these may be used alone, or two or more having different weight average molecular weights may be used in combination, and one or two or more prepolymers thereof. And may be used in combination.

Among these epoxy resins (A), an aralkyl type epoxy resin is particularly preferable. Thereby, the moisture absorption solder heat resistance and flame retardance of the resin substrate 100 can be further improved.
The aralkyl type epoxy resin is represented by the following formula (1), for example.

ここで、ＡおよびＢは、ベンゼン環、ビフェニル構造などの芳香族環を表す。またＡおよびＢの芳香族環の水素が置換されていてもよい。置換基としては、例えば、メチル基、エチル基、プロピル基、フェニル基などが挙げられる。ｎは繰返し単位を表し、例えば、１〜１０の整数である。

Here, A and B represent aromatic rings such as a benzene ring and a biphenyl structure. Moreover, the hydrogen of the aromatic ring of A and B may be substituted. Examples of the substituent include a methyl group, an ethyl group, a propyl group, and a phenyl group. n represents a repeating unit, for example, an integer of 1 to 10.

  Specific examples of the aralkyl type epoxy resin include the following (1a) and (1b).

（式中、ｎは、１〜５の整数を示す。）

(In the formula, n represents an integer of 1 to 5.)

（式中、ｎは、１〜５の整数を示す。）

(In the formula, n represents an integer of 1 to 5.)

  The epoxy resin (A) other than the above is preferably a novolac type epoxy resin having a condensed ring aromatic hydrocarbon structure. Thereby, heat resistance and low thermal expansibility can further be improved.

  The novolak type epoxy resin having a condensed ring aromatic hydrocarbon structure is a novolak type epoxy resin having a naphthalene, anthracene, phenanthrene, tetracene, chrysene, pyrene, triphenylene, and tetraphen or other condensed ring aromatic hydrocarbon structure. . The novolac type epoxy resin having a condensed ring aromatic hydrocarbon structure is excellent in low thermal expansion because a plurality of aromatic rings can be regularly arranged. Moreover, since the glass transition temperature is also high, it is excellent in heat resistance. Furthermore, since the molecular weight of the repeating structure is large, the flame retardancy is excellent as compared with the conventional novolac type epoxy resin.

  The novolak-type epoxy resin having a condensed ring aromatic hydrocarbon structure is obtained by epoxidizing a novolac-type phenol resin synthesized from a phenol compound, an aldehyde compound, and a condensed ring aromatic hydrocarbon compound.

  The phenol compound is not particularly limited, but examples thereof include cresols such as phenol, o-cresol, m-cresol, and p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2, 6-xylenol, 3,4-xylenol, xylenols such as 3,5-xylenol, trimethylphenols such as 2,3,5 trimethylphenol, ethyl such as o-ethylphenol, m-ethylphenol, p-ethylphenol Phenols, alkylphenols such as isopropylphenol, butylphenol, t-butylphenol, o-phenylphenol, m-phenylphenol, p-phenylphenol, catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene , 2,7-naphthalene diols such as dihydroxynaphthalene, resorcinol, catechol, hydroquinone, pyrogallol, polyhydric phenols such as fluoro Guru Singh, alkyl resorcinol, alkyl catechol, alkyl polyhydric phenols such as alkyl hydroquinone. Of these, phenol is preferable from the viewpoint of cost and the effect on the decomposition reaction.

  The aldehyde compound is not particularly limited, and examples thereof include formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, polyoxymethylene, chloral, hexamethylenetetramine, furfural, glyoxal, n-butyraldehyde, caproaldehyde, allylaldehyde, Examples include benzaldehyde, crotonaldehyde, acrolein, tetraoxymethylene, phenylacetaldehyde, o-tolualdehyde, salicylaldehyde, dihydroxybenzaldehyde, trihydroxybenzaldehyde, 4-hydroxy-3-methoxyaldehyde paraformaldehyde and the like.

  Although the condensed ring aromatic hydrocarbon compound is not particularly limited, for example, naphthalene derivatives such as methoxynaphthalene and butoxynaphthalene, anthracene derivatives such as methoxyanthracene, phenanthrene derivatives such as methoxyphenanthrene, other tetracene derivatives, chrysene derivatives, pyrene derivatives, Examples include triphenylene derivatives and tetraphen derivatives.

  The novolak type epoxy resin having a condensed ring aromatic hydrocarbon structure is not particularly limited. For example, methoxynaphthalene-modified ortho-cresol novolak epoxy resin, butoxynaphthalene-modified meta (para) cresol novolak epoxy resin, and methoxynaphthalene-modified novolak epoxy resin Etc. Among these, a novolac type epoxy resin having a condensed ring aromatic hydrocarbon structure represented by the following formula (V) is preferable.

(In the formula, Ar is a condensed ring aromatic hydrocarbon group, R may be the same or different from each other, and is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogen element, a phenyl group, A group selected from an aryl group such as a benzyl group and an organic group containing glycidyl ether, n, p and q are integers of 1 or more, and the values of p and q may be the same or different for each repeating unit. May be.)

(Ar in the formula (V) is a structure represented by (Ar1) to (Ar4) in the formula (VI), and Rs in the formula (VI) may be the same or different from each other. It is often a group selected from a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an aryl group such as a halogen element, a phenyl group and a benzyl group, and an organic group including glycidyl ether.)

  Further, as the epoxy resin (A) other than the above, naphthalene type epoxy resins such as naphthol type epoxy resin, naphthalene diol type epoxy resin, bifunctional to tetrafunctional epoxy type naphthalene resin, naphthylene ether type epoxy resin and the like are preferable. Thereby, the heat resistance and low thermal expansibility of the resin substrate 100 can be further improved. In addition, since the naphthalene ring has a higher π-π stacking effect than a benzene ring, it is particularly excellent in low thermal expansion and low thermal shrinkage. Further, since the polycyclic structure has a high rigidity effect and the glass transition temperature is particularly high, the change in heat shrinkage before and after reflow is small. As a naphthol type epoxy resin, for example, the following general formula (VII-1), as a naphthalene diol type epoxy resin, the following formula (VII-2), as a bifunctional or tetrafunctional epoxy type naphthalene resin, the following formula (VII-3): As (VII-4) (VII-5) and a naphthylene ether type epoxy resin, it can show by the following general formula (VII-6), for example.

（ｎは平均１以上６以下の数を示し、Ｒはグリシジル基または炭素数１以上１０以下の炭化水素基を示す。）

(N represents an average number of 1 to 6, and R represents a glycidyl group or a hydrocarbon group having 1 to 10 carbon atoms.)

（式中、Ｒ^１は水素原子またはメチル基を表し、Ｒ^２はそれぞれ独立的に水素原子、炭素原子数１〜４のアルキル基、アラルキル基、ナフタレン基、またはグリシジルエーテル基含有ナフタレン基を表し、ｏおよびｍはそれぞれ０〜２の整数であって、かつｏまたはｍの何れか一方は１以上である。）

(Wherein R ¹ represents a hydrogen atom or a methyl group, and R ² each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aralkyl group, a naphthalene group, or a glycidyl ether group-containing naphthalene group. , O and m are each an integer of 0 to 2, and either o or m is 1 or more.)

  Although the minimum of the weight average molecular weight (Mw) of an epoxy resin (A) is not specifically limited, Mw500 or more is preferable and especially Mw800 or more is preferable. It can suppress that tackiness arises in a prepreg (P) as Mw is more than the said lower limit. The upper limit of Mw is not particularly limited, but is preferably Mw 20,000 or less, and particularly preferably Mw 15,000 or less. When the Mw is not more than the above upper limit value, the impregnation property to the fiber base material is improved when the resin substrate 100 is produced, and a more uniform resin substrate 100 can be obtained. The Mw of the epoxy resin can be measured by GPC, for example.

  The content of the epoxy resin (A) contained in the epoxy resin composition (A) is not particularly limited as long as it is appropriately adjusted depending on the purpose, but the total solid content of the epoxy resin composition (A) (that is, , The component excluding the solvent) is 100% by mass, preferably 7.0% by mass to 30.0% by mass, and more preferably 8.0% by mass to 28.0% by mass. When the content of the epoxy resin (A) is not less than the above lower limit value, the handling property is improved and the first resin layer 103a can be easily formed. When the content of the epoxy resin (A) is not more than the above upper limit, the strength and flame retardancy of the resin substrate 100 are improved, the linear expansion coefficient of the resin substrate 100 is reduced, and the effect of reducing warpage is improved. There is a case.

  The content of the epoxy resin (A) contained in the epoxy resin composition (B) is not particularly limited as long as it is appropriately adjusted depending on the purpose, but the total solid content of the epoxy resin composition (B) (that is, , The component excluding the solvent) is 100% by mass, preferably 8.0% by mass to 40.0% by mass, and more preferably 10.0% by mass to 35.0% by mass. When the content of the epoxy resin (A) is not less than the above lower limit value, the handleability is improved and the second resin layer 103b can be easily formed. When the content of the epoxy resin (A) is not more than the above upper limit, the strength and flame retardancy of the resin substrate 100 are improved, the linear expansion coefficient of the resin substrate 100 is reduced, and the effect of reducing warpage is improved. There is a case.

  The epoxy resin compositions (A) and (B) according to this embodiment preferably further contain a bismaleimide compound (C). The maleimide group of the bismaleimide compound has a five-membered planar structure, and since the double bond of the maleimide group easily interacts between molecules and has high polarity, the compound has a maleimide group, a benzene ring, and other planar structures. It shows strong intermolecular interactions and can suppress molecular motion. Therefore, the epoxy resin compositions (A) and (B) can contain the bismaleimide compound (C), thereby reducing the linear expansion coefficient of the resulting resin substrate 100 and improving the glass transition temperature. Heat resistance can be improved.

As the bismaleimide compound (C), a bismaleimide compound (C-1) having at least two maleimide groups in the molecule is preferable.
Examples of the bismaleimide compound (C-1) include 4,4′-diphenylmethane bismaleimide, m-phenylene bismaleimide, p-phenylene bismaleimide, and 2,2-bis [4- (4-maleimidophenoxy) phenyl]. Propane, bis- (3-ethyl-5-methyl-4-maleimidophenyl) methane, 4-methyl-1,3-phenylenebismaleimide, N, N′-ethylenedimaleimide, N, N′-hexamethylenedimaleimide , Bis (4-maleimidophenyl) ether, bis (4-maleimidophenyl) sulfone, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, etc., compounds having two maleimide groups in the molecule 3 or more maleimide groups in the molecule such as polyphenylmethanemaleimide Such compounds, and the like.
One of these can be used alone, or two or more can be used in combination. Among these bismaleimide compounds (C-1), 4,4′-diphenylmethane bismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, bis, etc. because of its low water absorption. -(3-Ethyl-5-methyl-4-maleimidophenyl) methane and polyphenylmethanemaleimide are preferred.

  Moreover, as a bismaleimide compound (C), the reaction material of a bismaleimide compound (C-1) and an amine compound can also be used. As the amine compound, at least one selected from an aromatic diamine compound and a monoamine compound can be used.

  Examples of the aromatic diamine compound include o-dianisidine, o-tolidine, 3,3′-dihydroxy-4,4′-diaminobiphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, and 2,2 ′. -Dimethyl-4,4'-diaminobiphenyl, m-phenylenediamine, p-phenylenediamine, o-xylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 1,5-diaminonaphthalene, 4,4 ′-(p-phenylenediisopropylidene) dianiline, 2,2- [4- (4 -Aminophenoxy) phenyl] propane, 4,4'-diamino-3,3'-dimethyl-diphenylmethane, Examples thereof include bis (4- (4-aminophenoxy) phenyl) sulfone.

  Examples of the monoamine compound include o-aminophenol, m-aminophenol, p-aminophenol, o-aminobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, o-aminobenzenesulfonic acid, m-amino. Benzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline, o-aniline, m-aniline, p-aniline, o-methylaniline, m-methylaniline, p- Examples include methylaniline, o-ethylaniline, m-ethylaniline, p-ethylaniline, o-vinylaniline, m-vinylaniline, p-vinylaniline, o-allylaniline, m-allylaniline, p-allylaniline, and the like. It is done.

  Reaction of a bismaleimide compound (C-1) and an amine compound can be made to react in an organic solvent. The reaction temperature is, for example, 70 to 200 ° C., and the reaction time is, for example, 0.1 to 10 hours.

  The content of the bismaleimide compound (C) contained in the epoxy resin composition (A) is not particularly limited, but the total solid content of the epoxy resin composition (A) (that is, the component excluding the solvent) is 100% by mass. Is preferably 1.0% by mass or more and 25.0% by mass or less, and more preferably 5.0% by mass or more and 20.0% by mass or less. When the content of the bismaleimide compound (C) is within the above range, the elastic modulus of the resin substrate 100 can be further improved.

  The content of the bismaleimide compound (C) contained in the epoxy resin composition (B) is not particularly limited, but the total solid content of the epoxy resin composition (B) (that is, the component excluding the solvent) is 100% by mass. 15.0 mass% or more and 40.0 mass% or less is preferable, and 20.0 mass% or more and 38.0 mass% or less is more preferable. When the content of the bismaleimide compound (C) is not less than the above lower limit, the elastic modulus of the resin substrate 100 can be improved. When the content of the bismaleimide compound (C) is not more than the above upper limit value, the peel strength of the resin substrate 100 can be improved.

The epoxy resin compositions (A) and (B) according to this embodiment may contain a cyanate resin (D) instead of the bismaleimide compound (C), or a part of the bismaleimide compound (C) may be a cyanate resin. You may change to (D).
Although the said cyanate resin (D) is not specifically limited, For example, it can obtain by making a halogenated cyanide compound, phenols, and naphthol react, and prepolymerizing by methods, such as a heating, as needed. Moreover, the commercial item prepared in this way can also be used.
Epoxy resin composition (A) and (B) can make the linear expansion coefficient of the resin substrate 100 obtained small by further including cyanate resin (D) as a thermosetting resin. Furthermore, by using the cyanate resin (D), the electrical characteristics (low dielectric constant, low dielectric loss tangent), mechanical strength, and the like of the obtained resin substrate 100 can be improved.

  The cyanate resin (D) is, for example, a bisphenol cyanate resin such as a novolak type cyanate resin, a bisphenol A type cyanate resin, a bisphenol E type cyanate resin, or a tetramethylbisphenol F type cyanate resin; a naphthol aralkyl type phenol resin and a cyanogen halide. Naphthol aralkyl type cyanate resin obtained by the reaction with; dicyclopentadiene type cyanate resin; biphenylalkyl type cyanate resin. Among these, novolak type cyanate resins and naphthol aralkyl type cyanate resins are preferable, and novolak type cyanate resins are more preferable. By using a novolac-type cyanate resin, the crosslink density of the resin substrate 100 obtained increases, and heat resistance improves.

The reason for this is that the novolak cyanate resin forms a triazine ring after the curing reaction. Furthermore, it is considered that novolak-type cyanate resin has a high benzene ring ratio due to its structure and is easily carbonized. Moreover, the insulating layer containing a novolac type cyanate resin has excellent rigidity. Therefore, the heat resistance of the resin substrate 100 can be further improved.
As a novolak-type cyanate resin, what is shown by the following general formula (I) can be used, for example.

  The average repeating unit n of the novolak type cyanate resin represented by the general formula (I) is an arbitrary integer. The average repeating unit n is not particularly limited, but is preferably 1 or more, and more preferably 2 or more. When the average repeating unit n is not less than the above lower limit, the heat resistance of the novolak cyanate resin is improved, and it is possible to suppress the demerization and volatilization of the low mer during heating. The average repeating unit n is not particularly limited, but is preferably 10 or less, more preferably 7 or less. It can suppress that melt viscosity becomes it high that n is below the said upper limit, and the moldability of the resin substrate 100 can be improved.

  As the cyanate resin (D), a naphthol aralkyl type cyanate resin represented by the following general formula (II) is also preferably used. The naphthol aralkyl type cyanate resin represented by the following general formula (II) includes, for example, naphthols such as α-naphthol or β-naphthol, p-xylylene glycol, α, α′-dimethoxy-p-xylene, 1,4 -It is obtained by condensing a naphthol aralkyl type phenol resin obtained by reaction with di (2-hydroxy-2-propyl) benzene and cyanogen halide. The repeating unit n of the general formula (II) is preferably an integer of 10 or less. When the repeating unit n is 10 or less, a more uniform insulating layer can be obtained. In addition, intramolecular polymerization hardly occurs at the time of synthesis, the liquid separation property at the time of washing with water tends to be improved, and the decrease in yield tends to be prevented.

（式中、Ｒは水素原子またはメチル基を示し、ｎは１以上１０以下の整数を示す。）

(In the formula, R represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 10.)

  Moreover, cyanate resin (D) may be used individually by 1 type, may use 2 or more types together, and may use 1 type, 2 or more types, and those prepolymers together.

  Although content of cyanate resin (D) contained in an epoxy resin composition (A) is not specifically limited, The total solid content (namely, component except a solvent) of an epoxy resin composition (A) is 100 mass%. 1.0 mass% or more and 25.0 mass% or less is preferable, and 5.0 mass% or more and 20.0 mass% or less are more preferable. When the content of the cyanate resin (D) is within the above range, the elastic modulus of the resin substrate 100 can be further improved.

  The content of the cyanate resin (D) contained in the epoxy resin composition (B) is not particularly limited, but the total solid content of the epoxy resin composition (B) (that is, the component excluding the solvent) is 100% by mass. When it is, 15.0 mass% or more and 40.0 mass% or less are preferable, and 20.0 mass% or more and 38.0 mass% or less are more preferable. The elastic modulus of the resin substrate 100 can be improved as content of cyanate resin (D) is more than the said lower limit. When the content of the cyanate resin (D) is not more than the above upper limit value, the peel strength of the resin substrate 100 can be improved.

The epoxy resin compositions (A) and (B) according to this embodiment contain an inorganic filler (B) as an essential component. Thereby, the storage elastic modulus E ′ of the resin substrate 100 can be improved. Furthermore, the linear expansion coefficient of the resin substrate 100 can be reduced.
Examples of the inorganic filler (B) include silicates such as talc, fired clay, unfired clay, mica and glass; oxides such as titanium oxide, alumina, boehmite, silica and fused silica; calcium carbonate and magnesium carbonate Carbonates such as hydrotalcite; hydroxides such as aluminum hydroxide, magnesium hydroxide and calcium hydroxide; sulfates or sulfites such as barium sulfate, calcium sulfate and calcium sulfite; zinc borate, barium metaborate, Borates such as aluminum borate, calcium borate and sodium borate; nitrides such as aluminum nitride, boron nitride, silicon nitride and carbon nitride; titanates such as strontium titanate and barium titanate it can.
Among these, talc, alumina, glass, silica, mica, aluminum hydroxide, and magnesium hydroxide are preferable. As the inorganic filler (B), one of these may be used alone, or two or more may be used in combination.

  The average particle diameter of the inorganic filler (B2) contained in the epoxy resin composition (A) is preferably 0.04 μm or more and less than 5.0 μm, more preferably 0.1 μm or more and 1.3 μm or less, Preferably they are 0.2 micrometer or more and 0.8 micrometer or less. When the average particle diameter of the inorganic filler (B2) is not less than the above lower limit value, it is possible to suppress the viscosity of the varnish from being increased, and the workability at the time of producing the first resin layer 103a can be improved. When the average particle diameter of the inorganic filler (B2) is not more than the above upper limit, phenomena such as sedimentation of the inorganic filler (B2) in the varnish can be suppressed, and a more uniform first resin layer 103a can be obtained. .

  The average particle diameter of the inorganic filler (B1) contained in the epoxy resin composition (B) is preferably 0.04 μm or more and 5.0 μm or less, more preferably 0.2 μm or more and 3.0 μm or less, Preferably they are 1.0 micrometer or more and 2.5 micrometers or less. When the average particle diameter of the inorganic filler (B1) is not less than the above lower limit, it is possible to suppress the viscosity of the varnish from being increased, and workability at the time of producing the first resin layer 103b can be improved. When the average particle diameter of the inorganic filler (B1) is not more than the above upper limit, phenomena such as sedimentation of the inorganic filler (B1) in the varnish can be suppressed, and a more uniform second resin layer 103b can be obtained. .

The average particle size of the inorganic filler (B) is measured, for example, by measuring the particle size distribution on a volume basis using a laser diffraction particle size distribution measuring device (LA-500, manufactured by HORIBA), and the median diameter (D ₅₀ ). Can be the average particle size.

  Further, the inorganic filler (B) is not particularly limited, but an inorganic filler having a monodispersed average particle diameter may be used, or an inorganic filler having a polydispersed average particle diameter may be used. Furthermore, one type or two or more types of inorganic fillers having an average particle size of monodispersed and / or polydispersed may be used in combination.

  In the epoxy resin composition (A), the content of the inorganic filler (B2) is 50.0 when the total solid content of the epoxy resin composition (A) (that is, the component excluding the solvent) is 100% by mass. The mass% is preferably 90.0 mass% or less, and more preferably 55.0 mass% or more and 80.0 mass% or less.

  In the epoxy resin composition (B), the content of the inorganic filler (B1) is 20.0 when the total solid content of the epoxy resin composition (B) (that is, the component excluding the solvent) is 100% by mass. The mass% is preferably 60.0 mass% or less, and more preferably 25.0 mass% or more and 55.0 mass% or less.

  In addition, a hardening | curing agent and a coupling agent can be suitably mix | blended with an epoxy resin composition (A) and (B) as needed.

Examples of the curing agent include tertiary amine compounds such as benzyldimethylamine (BDMA) and 2,4,6-trisdimethylaminomethylphenol (DMP-30); 2-methylimidazole, 2-ethyl-4-methylimidazole (EMI24), 2-phenyl-4-methylimidazole (2P4MZ), 2-phenylimidazole (2PZ), 2-phenyl-4-methyl-5-hydroxyimidazole (2P4MHZ), 1-benzyl-2-phenylimidazole (1B2PZ) ) And the like; and catalyst-type curing agents such as Lewis acids such as BF ₃ complexes.
In addition, for example, aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), and metaxylylenediamine (MXDA), m-phenylenediamine, p-phenylenediamine, o-xylenediamine, 4,4′- Diaminodiphenylmethane, 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 1,5-diaminonaphthalene, 4,4′- (P-phenylenediisopropylidene) dianiline, 2,2- [4- (4-aminophenoxy) phenyl] propane, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-diamino-3 , 3′-diethyl-5,5′-dimethyldiphenylmethane, 3 In addition to aromatic polyamines such as 3′-diethyl-4,4′-diaminodiphenylmethane, polyamine compounds including dicyandiamide (DICY), organic acid dihydrazide, etc .; hexahydrophthalic anhydride (HHPA), methyltetrahydrophthalic anhydride (MTHPA) Acid anhydrides including aromatic acid anhydrides such as alicyclic acid anhydrides such as, trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), benzophenone tetracarboxylic acid (BTDA); polysulfide, thioester, Polymercaptan compounds such as thioethers; Isocyanate compounds such as isocyanate prepolymers and blocked isocyanates; polyaddition type curing agents such as organic acids such as carboxylic acid-containing polyester resins; 2,2′-methylenebis (4-ethyl-6- t ert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4′-thiobis (3- Methyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butylhydroquinone, 1,3,5-tris (3,5-di-tert) Phenolic compounds such as -butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) trione can also be used.

Furthermore, for example, phenolic resin-based curing agents such as novolak-type phenolic resins and resol-type phenolic resins; urea resins such as methylol group-containing urea resins; and condensation-type curing agents such as melamine resins such as methylol group-containing melamine resins It may be used.
The phenol resin-based curing agent is a monomer, oligomer, or polymer in general having two or more phenolic hydroxyl groups in one molecule, and its molecular weight and molecular structure are not particularly limited. For example, phenol novolak resin, cresol novolak Resins, naphthol novolak resins and other novolac phenol resins; trifunctional methane type phenol resins and other polyfunctional phenol resins; terpene modified phenol resins and dicyclopentadiene modified phenol resins and other modified phenol resins; phenylene skeleton and / or biphenylene skeleton Aralkyl-type resins such as phenol aralkyl resins having phenylene and / or naphthol aralkyl resins having a biphenylene skeleton; bisphenols such as bisphenol A and bisphenol F Is like compounds, they may be used in combination of two or more be used one kind alone. Among these, the hydroxyl equivalent is preferably 90 g / eq or more and 250 g / eq or less from the viewpoint of curability.
The weight average molecular weight of the phenol resin is not particularly limited, but is preferably 4 × 10 ^{2 to} 1.8 × 10 ^{3 and} more preferably 5 × 10 ^{2 to} 1.5 × 10 ³ . By making the weight average molecular weight equal to or higher than the above lower limit value, problems such as tackiness occur in the prepreg, and by making the above upper limit value or less, the impregnation property to the fiber base material is improved at the time of prepreg production, A more uniform product can be obtained.

  In the epoxy resin composition (A), the content of the curing agent is not particularly limited, but is 0 when the total solid content of the epoxy resin composition (A) (that is, the component excluding the solvent) is 100% by mass. 0.01 mass% or more and 15.0 mass% or less is preferable, and 0.1 mass% or more and 10.0 mass% or less is more preferable. When the content of the curing agent is not less than the above lower limit, the effect of promoting curing can be sufficiently exhibited. The preservability of a prepreg can be improved more as content of a hardening | curing agent is below the said upper limit.

  In the epoxy resin composition (B), the content of the curing agent is not particularly limited, but is 0 when the total solid content of the epoxy resin composition (B) (that is, the component excluding the solvent) is 100% by mass. It is preferably 1% by mass or more and 20.0% by mass or less, and more preferably 0.5% by mass or more and 15.0% by mass or less. When the content of the curing agent is not less than the above lower limit, the effect of promoting curing can be sufficiently exhibited. The preservability of a prepreg can be improved more as content of a hardening | curing agent is below the said upper limit.

  Furthermore, the epoxy resin compositions (A) and (B) may contain a coupling agent. By using the coupling agent, the wettability of the interface between the fiber substrate or the inorganic filler (B) and each resin can be improved. Therefore, it is preferable to use a coupling agent, and the heat resistance of the resin substrate 100 can be improved.

Examples of the coupling agent include silane coupling agents such as epoxy silane coupling agents, cationic silane coupling agents, and amino silane coupling agents, titanate coupling agents, and silicone oil type coupling agents. A coupling agent may be used individually by 1 type, and may use 2 or more types together.
Thereby, the wettability of the interface of a fiber base material or an inorganic filler (B) and each resin can be made high, and, thereby, the heat resistance of the resin substrate 100 can be improved more.

The addition amount of the coupling agent is not particularly limited because it depends on the specific surface area of the inorganic filler (B), but the total solid content of the epoxy resin compositions (A) and (B) (that is, the component excluding the solvent) is not limited. When it is 100 mass%, 0.01 mass% or more and 1 mass% or less are preferable, and 0.05 mass% or more and 0.5 mass% or less are more preferable.
When the content of the coupling agent is not less than the above lower limit, the inorganic filler (B) can be sufficiently covered, and the heat resistance of the resin substrate 100 can be improved. Moreover, it can suppress that reaction influences that content of a coupling agent is below the said upper limit, and can suppress the fall of the bending strength of the resin substrate 100, etc.

  Furthermore, the epoxy resin compositions (A) and (B) are provided with pigments, dyes, antifoaming agents, leveling agents, ultraviolet absorbers, foaming agents, antioxidants, flame retardants, as long as the object of the present invention is not impaired. In addition, additives other than the above components such as an ion scavenger may be added.

  Examples of pigments include kaolin, synthetic iron oxide red, cadmium yellow, nickel titanium yellow, strontium yellow, hydrous chromium oxide, chromium oxide, cobalt aluminate, synthetic ultramarine blue and other inorganic pigments, phthalocyanine polycyclic pigments, azo pigments, etc. Etc.

  Examples of the dye include isoindolinone, isoindoline, quinophthalone, xanthene, diketopyrrolopyrrole, perylene, perinone, anthraquinone, indigoid, oxazine, quinacridone, benzimidazolone, violanthrone, phthalocyanine, azomethine and the like.

Epoxy resin compositions (A) and (B) are acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, ethyl acetate, cyclohexane, heptane, cyclohexane, cyclohexanone, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethylene glycol, cellosolve type In organic solvents such as carbitol, anisole, N-methylpyrrolidone, ultrasonic dispersion method, high-pressure collision dispersion method, high-speed rotation dispersion method, bead mill method, high-speed shear dispersion method, and rotation and revolution dispersion method It can melt | dissolve, mix and stir using various mixers, and can be set as resin varnish (I).
The solid content of the resin varnish (I) is not particularly limited, but is preferably 40% by mass or more and 80% by mass or less, and particularly preferably 50% by mass or more and 70% by mass or less. Thereby, the impregnation property to the fiber base material of resin varnish (I) can further be improved.

In the above epoxy resin composition (A), the ratio of each component is as follows, for example.
When the total solid content of the epoxy resin composition (A) (that is, the component excluding the solvent) is 100% by mass, the proportion of the epoxy resin (A) is preferably 7.0% by mass or more and 30.0% by mass or less. The ratio of at least one selected from the bismaleimide compound (C) and the cyanate resin (D) is 1.0% by mass or more and 25.0% by mass or less, and the ratio of the inorganic filler (B2) is 50.%. It is 0 mass% or more and 90.0 mass% or less.
More preferably, the ratio of the epoxy resin (A) is 8.0% by mass or more and 28.0% by mass or less, and the ratio of at least one selected from the bismaleimide compound (C) and the cyanate resin (D) is 5. It is 0 mass% or more and 20.0 mass% or less, and the ratio of an inorganic filler (B2) is 55.0 mass% or more and 80.0 mass% or less.

Moreover, in an epoxy resin composition (B), the ratio of each component is as follows, for example.
When the total solid content (that is, the component excluding the solvent) of the epoxy resin composition (B) is 100% by mass, the ratio of the epoxy resin (A) is preferably 8.0% by mass or more and 40.0% by mass or less. The ratio of at least one selected from the bismaleimide compound (C) and the cyanate resin (D) is 15.0 mass% or more and 40.0 mass% or less, and the ratio of the inorganic filler (B1) is 20. It is 0 mass% or more and 60.0 mass% or less.
More preferably, the ratio of the epoxy resin (A) is 10.0% by mass or more and 35.0% by mass or less, and the ratio of at least one selected from the bismaleimide compound (C) and the cyanate resin (D) is 20. It is 0 mass% or more and 38.0 mass% or less, and the ratio of an inorganic filler (B1) is 25.0 mass% or more and 55.0 mass% or less.

  The fiber substrate is not particularly limited, but glass fiber substrates such as glass cloth and glass nonwoven fabric, polyamide resin fibers, aromatic polyamide resin fibers, polyamide resin fibers such as wholly aromatic polyamide resin fibers, polyester resin fibers, Synthetic fiber substrate, kraft paper, composed of woven or non-woven fabric mainly composed of aromatic polyester resin fiber, polyester resin fiber such as wholly aromatic polyester resin fiber, polyimide resin fiber, fluororesin fiber, Examples thereof include organic fiber substrates such as cotton linter paper or a paper substrate mainly composed of linter and kraft pulp mixed paper. Any of these can be used. Among these, a glass fiber base material is preferable. Thereby, the resin substrate 100 having low water absorption, high strength, and low thermal expansion can be obtained.

Although the thickness of a fiber base material is not specifically limited, Preferably it is 5 micrometers or more and 150 micrometers or less, More preferably, they are 10 micrometers or more and 100 micrometers or less, More preferably, they are 12 micrometers or more and 90 micrometers or less. By using the fiber base material having such a thickness, the handling property at the time of producing the prepreg can be further improved.
When the thickness of the fiber base material is not more than the above upper limit value, the impregnation property of the epoxy resin composition (A) in the fiber base material can be improved, and the occurrence of strand voids and a decrease in insulation reliability can be suppressed. In addition, it is possible to easily form a through hole by a laser such as carbon dioxide, UV, or excimer. Moreover, the intensity | strength of a fiber base material or a prepreg can be improved as the thickness of a fiber base material is more than the said lower limit. As a result, handling properties can be improved, prepreg can be easily manufactured, and warpage of the resin substrate 100 can be suppressed.

The fiber base material used in the present embodiment, the basis weight is preferably (1m weight of the fiber base material per ²⁾ is 150 g / ^{m 2} or less 4g / ^{m 2} or more, 8 g / ^{m 2} or more 120 g / ^{m 2} Or less, more preferably 12 g / m ² or more and 100 g / m ² or less, further preferably 12 g / m ² or more and 60 g / m ² or less, more preferably 12 g / m ² or more and 30 g / m ² or less. It is particularly preferred that it is ² or less.

  When the basis weight is not more than the above upper limit value, the impregnation property of the epoxy resin composition (A) in the fiber base material is improved, and the occurrence of strand voids and a decrease in insulation reliability can be suppressed. In addition, it is possible to easily form a through hole by a laser such as carbon dioxide, UV, or excimer. Moreover, the intensity | strength of a fiber base material or a prepreg can be improved as basic weight is more than the said lower limit. As a result, handling properties can be improved, prepreg can be easily manufactured, and warpage of the resin substrate 100 can be suppressed.

  As the glass fiber substrate, for example, a glass fiber substrate made of E glass, S glass, D glass, T glass, NE glass, UT glass, L glass, HP glass, quartz glass, or the like is preferably used.

  Next, the printed wiring board 300 according to the present embodiment will be described. 5 and 6 are cross-sectional views showing an example of the configuration of the printed wiring board 300 in the present embodiment.

  The printed wiring board 300 includes at least an insulating layer 301 provided with a via hole 307 and a metal layer 303 provided on at least one surface of the insulating layer 301. In the present embodiment, the via hole 307 is a hole for electrically connecting the layers, and may be either a through hole or a non-through hole.

As shown in FIG. 5, the printed wiring board 300 according to the present embodiment may be a single-sided printed wiring board, a double-sided printed wiring board, or a multilayer printed wiring board. A double-sided printed wiring board is a printed wiring board in which a metal layer 303 is laminated on both sides of an insulating layer 301. The multilayer printed wiring board is a print in which two or more metal layers 303 are stacked on an insulating layer 301 via an interlayer insulating layer (also referred to as a build-up layer) by a plated through hole method, a build-up method, or the like. It is a wiring board.
Here, in the printed wiring board 300 according to the present embodiment, the insulating layer 301 corresponds to the resin substrate 100 according to the present embodiment, and corresponds to the insulating layer 301 of the metal-clad laminate 200.

  The metal layer 303 is, for example, a circuit layer, and includes an electroless metal plating film 308 and an electrolytic metal plating layer 309.

  When the printed wiring board 300 is a multilayer printed wiring board as shown in FIG. 6, the metal layer 303 is a circuit layer in the core layer 311 or the buildup layer 317.

  The metal layer 303 is formed by, for example, the SAP (semi-additive process) method on the surface of the insulating layer 301 that has been subjected to chemical treatment or plasma treatment. After the electroless plating film 308 is applied on the insulating layer 301, the non-circuit forming portion is protected by a plating resist, the electrolytic metal plating layer 309 is applied by electrolytic plating, and the electroless metal plating is removed by removing the plating resist and flash etching. The metal layer 303 is formed over the insulating layer 301 by removing the film 308.

  The circuit dimension of the metal layer 303 can be 25 μm / 25 μm or less, particularly 15 μm / 15 μm or less, when expressed in line and space (L / S). If the circuit dimensions are reduced and the wiring is made fine, the adhesiveness decreases and the insulation reliability between the wirings decreases. However, the printed wiring board 300 according to the present embodiment is capable of fine wiring with a line and space (L / S) of 15 μm / 15 μm or less, and the line and space (L / S) can be refined to about 10 μm / 10 μm. Can be achieved.

  The thickness of the metal layer 303 is not particularly limited, but is usually 5 μm or more and 25 μm or less.

The insulating layer 305 in the buildup layer 317 is not particularly limited as long as it is made of an insulating material. For example, the insulating layer 305 can be made of either a resin film or a prepreg. Among these, the prepreg is a sheet-like material and has excellent dielectric properties, various properties such as mechanical and electrical connection reliability under high temperature and high humidity, and is suitable for manufacturing a build-up layer 317 for a printed wiring board. preferable.
As the prepreg, the prepreg (P) described above is particularly preferable.

  The thickness of the insulating layer 301 in the core layer 311 (including the insulating layer 301 in the printed wiring board 300 not including the build-up layer 317) is preferably 0.025 mm or more and 0.1 mm or less. When the thickness of the insulating layer 301 is within the above range, the balance between mechanical strength and productivity is particularly excellent, and the insulating layer 301 suitable for a thin printed wiring board can be obtained.

  The thickness of the insulating layer 305 in the buildup layer 317 is preferably 0.015 mm or more and 0.05 mm or less. When the thickness of the insulating layer 305 is within the above range, the balance between mechanical strength and productivity is particularly excellent, and the insulating layer 305 suitable for a thin printed wiring board can be obtained.

  Next, an example of a method for manufacturing the printed wiring board 300 will be described. However, the method for manufacturing the printed wiring board 300 according to the present embodiment is not limited to the following example.

First, the metal-clad laminate 200 is prepared.
Next, the metal foil 105 is removed by etching.

Next, a via hole 307 is formed in the insulating layer 301. The via hole 307 can be formed using, for example, a drilling machine or laser irradiation. Examples of the laser used for laser irradiation include an excimer laser, a UV laser, and a carbon dioxide gas laser. Resin residues after forming the via hole 307 may be removed by an oxidizing agent such as permanganate or dichromate.
Note that the via hole 307 may be formed in the insulating layer 301 before the metal foil 105 is removed by the etching treatment.

Next, a chemical treatment or a plasma treatment is performed on the surface of the insulating layer 301.
The chemical treatment is not particularly limited, and examples thereof include a method using an oxidant solution having an organic substance decomposing action. Examples of the plasma treatment include a method of removing organic residue by irradiating a target with an active species (plasma, radical, etc.) having a strong oxidizing action directly.

  Next, the metal layer 303 is formed. The metal layer 303 can be formed by, for example, a semi-additive process. This will be specifically described below.

  First, an electroless metal plating film 308 is formed on the surface of the insulating layer 301 and the via hole 307 by using an electroless plating method, so that both sides of the printed wiring board 300 are electrically connected. The via hole 307 can be appropriately filled with a conductor paste or a resin paste. An example of the electroless plating method will be described. For example, first, catalyst nuclei are provided on the surface of the insulating layer 301. The catalyst nucleus is not particularly limited. For example, a noble metal ion or palladium colloid can be used. Subsequently, an electroless metal plating film 308 is formed by electroless plating using the catalyst nucleus as a nucleus. For the electroless plating treatment, for example, one containing copper sulfate, formalin, complexing agent, sodium hydroxide, or the like can be used. In addition, it is preferable to heat-process 100-250 degreeC after electroless plating, and to stabilize a plating film. A heat treatment at 120 to 180 ° C. is particularly preferable in that a film capable of suppressing oxidation can be formed. Moreover, the average thickness of the electroless metal plating film 308 is, for example, about 0.1 to 2 μm.

  Next, a plating resist having a predetermined opening pattern is formed on the electroless metal plating film 308. This opening pattern corresponds to, for example, a circuit pattern. The plating resist is not particularly limited, and known materials can be used, but liquid and dry films can be used. In the case of forming fine wiring, it is preferable to use a photosensitive dry film or the like as the plating resist. An example using a photosensitive dry film will be described. For example, a photosensitive dry film is laminated on the electroless metal plating film 308, the non-circuit formation region is exposed and photocured, and the unexposed portion is dissolved and removed with a developer. A plating resist is formed by leaving the cured photosensitive dry film.

  Next, an electrolytic metal plating layer 309 is formed by electroplating at least inside the opening pattern of the plating resist and on the electroless metal plating film 308. The electroplating treatment is not particularly limited, but a known method used for ordinary printed wiring boards can be used. For example, in a state where the plating solution is immersed in a plating solution such as copper sulfate, an electric current is supplied to the plating solution. A method such as flowing can be used. The electrolytic metal plating layer 309 may be a single layer or may have a multilayer structure. The material of the electrolytic metal plating layer 309 is not particularly limited, and for example, any one or more of copper, copper alloy, 42 alloy, nickel, iron, chromium, tungsten, gold, and solder can be used.

  Next, the plating resist is removed using an alkaline stripping solution, sulfuric acid, or a commercially available resist stripping solution.

  Next, the electroless metal plating film 308 other than the region where the electrolytic metal plating layer 309 is formed is removed. For example, the electroless metal plating film 308 can be removed by using soft etching (flash etching) or the like. Here, the soft etching treatment can be performed, for example, by etching using an etchant containing sulfuric acid and hydrogen peroxide. Thereby, the metal layer 303 can be formed. The metal layer 303 is composed of an electroless metal plating film 308 and an electrolytic metal plating layer 309.

  Furthermore, a build-up layer can be stacked on the printed wiring board 300 as necessary, and the steps of interlayer connection and circuit formation by a semi-additive process can be repeated to form a multilayer.

  The printed wiring board 300 of this embodiment is obtained by the above.

  Next, the semiconductor device 400 according to the present embodiment will be described. 7 and 8 are cross-sectional views showing an example of the configuration of the semiconductor device 400 according to the embodiment of the present invention. The printed wiring board 300 can be used in a semiconductor device 400 as shown in FIGS. A method for manufacturing the semiconductor device 400 is not particularly limited, and examples thereof include the following methods.

  First, a build-up layer is laminated on the metal layer 303 as necessary, and the steps of interlayer connection and circuit formation by a semi-additive process are repeated. And the soldering resist layer 401 is laminated | stacked on the both surfaces or single side | surface of the printed wiring board 300 as needed.

  The method of forming the solder resist layer 401 is not particularly limited. For example, a method of forming by laminating, exposing and developing a dry film type solder resist, or exposing and developing a liquid resist printed This is done by the forming method.

  Subsequently, by performing a reflow process, the semiconductor element 407 is fixed onto the connection terminal which is a part of the wiring pattern via the solder bump 410. Thereafter, the semiconductor device 400 as shown in FIGS. 7 and 8 is obtained by sealing the semiconductor element 407, the solder bump 410, and the like with the sealing material 413.

As mentioned above, although embodiment of this invention was described, these are illustrations of this invention and various structures other than the above are also employable. For example, in the present embodiment, the case where the prepreg is a single layer is shown, but the resin substrate 100 may be manufactured using a laminate of two or more prepregs.
Moreover, in the said embodiment, although the semiconductor element 407 and the printed wiring board 300 were connected by the solder bump 410, it is not restricted to this. For example, the semiconductor element 407 and the printed wiring board 300 may be connected by a bonding wire.

  Hereinafter, although an example and a comparative example explain the present invention, the present invention is not limited to these. In addition, in an Example, unless otherwise specified, a part represents a mass part. Moreover, each thickness is represented by the average film thickness.

Example 1
(1) Preparation of resin varnish (A) 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (manufactured by Keisei Kasei Co., Ltd., BMI-80, double bond equivalent 285) 17.5 parts by mass, naphthol Modified novolak epoxy resin (Nippon Kayaku Co., Ltd., NC-7000L, epoxy equivalent 230, epoxy resin represented by the above formula (VII-1) n = 1.7, R is glycidyl group) 14.1 parts by mass, 3 , 3′-diethyl-4,4′-diaminodiphenylmethane (Nippon Kayaku Co., Ltd., Kayahard AA amine equivalent 63.5) 7.8 parts by mass, 4,4′-butylidenebis (3-methyl-6-tert) -Butylphenol) (Ouchi Shinsei Chemical, NOCRACK NS-30) 0.3 parts by mass, epoxy silane coupling agent (Momentive Performance Materials, A1 7) 0.2 parts by mass, silica particles (manufactured by Admatechs, SO-C1, average particle size 0.25 μm) N-methylpyrrolidone was added to 60.0 parts by mass to adjust the nonvolatile content to 65%, The resin varnish (A) was prepared by stirring using a high-speed stirring device.

(2) Production of first resin layer-attached film (A) The resin varnish (A) obtained in (1) was converted into a polyethylene terephthalate (PET) film (Mitsubishi Chemical Polyester, SFB-38, thickness 38 μm, width). 480 m) was applied on one side using a comma coater so that the resin layer after drying (after semi-curing) had a thickness of 25 μm. Subsequently, this was dried with a 120 degreeC drying apparatus for 10 minutes, and the film (A) with a 1st resin layer was produced.

(3) Production of prepreg (P1) Glass cloth (cross type # 1027, width 360 mm, thickness 20 μm, E glass, basis weight 19 g / m ² ) was used as a fiber base material, and the prepreg was prepared by a vacuum laminating apparatus and a hot air drying apparatus. Manufactured.
Specifically, the film with the first resin layer (A) is overlapped on both surfaces of the glass cloth so that they are positioned at the center in the width direction of the glass cloth, and an 80 ° C. laminating roll is placed under a reduced pressure of 1330 Pa. And joined. The tension applied to the glass cloth was 200 N / m.
Here, in the inner area of the width direction dimension of the glass cloth, the resin layer of the film with the first resin layer (A) is bonded to both sides of the glass cloth, and in the outer area of the width direction dimension of the glass cloth. The resin layers of the film with the first resin layer (A) were joined together.
Next, the above-mentioned joined piece was heated for 2 minutes through a horizontal conveyance type hot air drying apparatus set at 120 ° C. without applying pressure, and a thickness of 60 μm (however, the thickness of the PET film was reduced). Excluding) A prepreg (P1) with a double-sided PET film (first resin layer: 20 μm, fiber base layer: 20 μm, first resin layer: 20 μm) was obtained.

(4) Preparation of resin varnish (B) 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (KMI Kasei Co., Ltd. BMI-80, double bond equivalent 285) 30.2 parts by mass, naphthalenediol Type epoxy resin (manufactured by DIC, HP-4032D, epoxy equivalent 150) 15.9 parts by mass, 3,3′-diethyl-4,4′-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd., Kayahard AA amine equivalent 63 .5) 13.4 parts by mass, 4,4′-butylidenebis (3-methyl-6-tert-butylphenol) (Ouchi Shinsei Chemical Co., Ltd., NOCRACK NS-30) 0.3 parts by mass, epoxy silane coupling agent (Momentive Performance Materials, Inc., A187) 0.2 parts by mass, silica particles (manufactured by Admatechs, SO-C5, average particle size 1. [mu] m) to 40.0 parts by weight of N- methylpyrrolidone was added was adjusted to a nonvolatile content of 65% to prepare a resin varnish (B) with stirring using a high speed stirrer.

(5) Production of second resin layer-attached film (B) The resin varnish (B) obtained in (4) was converted into a polyethylene terephthalate (PET) film (Mitsubishi Chemical Polyester, SFB-38, thickness 38 μm, width). On one side of 480 m), coating was performed using a comma coater so that the thickness of the resin layer after drying (after semi-curing) was 5 μm. Subsequently, this was dried with a 120 degreeC drying apparatus for 10 minutes, and the film (B) with a resin layer was produced.

(6) Preparation of prepreg (P) The PET film of prepreg (P1) with double-sided PET film obtained in (3) was peeled off, and the film with the second resin layer (B) obtained in (5) on both sides These were joined together under a reduced pressure of 1330 Pa using a laminate roll at 80 ° C. using a vacuum laminator and a hot air dryer. Next, the bonded material was heat-treated without applying pressure by passing it through a horizontal conveyance type hot air drying apparatus set at 120 ° C. for 2 minutes to obtain a thickness of 70 μm (however, the thickness of the PET film was reduced). Excluding) (second resin layer: 5 μm, first resin layer: 20 μm, fiber substrate layer: 20 μm, first resin layer: 20 μm, second resin layer: 5 μm) A prepreg (P) with a double-sided PET film is obtained. It was.

(7) Preparation of metal-clad laminate The PET films on both sides of the prepreg (P) with a double-sided PET film obtained in (6) were peeled off. Subsequently, the two prepregs (P) were overlaid, and 2 μm copper foil (NSAP-2B, manufactured by Nippon Electrolytic Co., Ltd.) was overlaid on both sides. Next, the laminate was sandwiched between smooth metal plates and subjected to heat and pressure molding under conditions of a temperature of 220 ° C. and a pressure of 4 MPa for 2 hours. Next, while maintaining the pressure of 4 MPa, the metal-clad laminate was obtained by cooling to 30 ° C. at a rate of temperature decrease of 5 ° C./min. The thickness of the insulating layer (part excluding the copper foil) of the obtained metal-clad laminate was 0.140 mm.

(8) Production of printed wiring board The copper foil of the metal-clad laminate of (7) was removed by etching. Next, a through hole (through hole) was formed by a carbonic acid laser. Next, the inside of the through hole and the surface of the insulating layer were immersed in a swelling liquid at 60 ° C. (Atotech Japan, Swelling Dip Securigant P) for 5 minutes, and further an aqueous potassium permanganate solution at 80 ° C. (Atotech Japan, It was immersed in Concentrate Compact CP) for 15 minutes and then neutralized and roughened.
After passing through the steps of degreasing, applying a catalyst, and activating the electroless copper plating film, the electroless copper plating film is formed to have a plating resist formation, and the electroless copper plating film is used as a power feeding layer to form a pattern electroplated copper of 12 μm. L / S = 12/12 μm fine circuit processing was performed. Next, an annealing process was performed at 200 ° C. for 60 minutes with a hot air drying apparatus, and then the power feeding layer was removed by flash etching.
Next, a solder resist (manufactured by Taiyo Ink Manufacturing Co., Ltd., PSR-4000 AUS703) is printed, exposed with a predetermined mask so that the semiconductor element mounting pad and the like are exposed, developed and cured, and the solder resist on the circuit The layer was formed to have a thickness of 12 μm.
Finally, on the circuit layer exposed from the solder resist layer, an electroless nickel plating layer of 3 μm and a plating layer of 0.1 μm of the electroless gold plating layer were further formed to obtain a printed wiring board. .

(9) Fabrication of Semiconductor Device A semiconductor device is a semiconductor device (TEG chip, size 8 mm × 8 mm, thickness 0.1 mm) having solder bumps on the printed wiring board obtained in (8), using a flip chip bonder device. It was mounted by thermocompression bonding. Next, after solder bumps were melt bonded in an IR reflow furnace, a liquid sealing resin (manufactured by Sumitomo Bakelite Co., Ltd., CRP-4160G) was filled and the liquid sealing resin was cured to obtain a semiconductor device. The liquid sealing resin was cured at a temperature of 150 ° C. for 120 minutes. As the solder bumps of the semiconductor element, those formed of eutectic of Sn / Pb composition were used. Finally, it was separated into pieces of 14 mm × 14 mm with a router to obtain a semiconductor device.

(10) Peel strength The copper foil is removed from the metal-clad laminate obtained in (7) by etching, and immersed in a swelling solution at 60 ° C. (Swelling Dip Securigant P, manufactured by Atotech Japan) for 5 minutes, and further 80 After being immersed in a potassium permanganate aqueous solution (manufactured by Atotech Japan Co., Ltd., Concentrate Compact CP) at 15 ° C. for 15 minutes, it was neutralized and roughened. After going through the steps of degreasing, applying a catalyst and activating this, an electroless copper plating film was formed to about 1 μm and electroplated copper was formed to 30 μm, and annealing treatment was performed at 200 ° C. for 60 minutes in a hot air drying apparatus. A 100 mm × 20 mm test piece was prepared based on JIS-C-6481, and the peel strength at 23 ° C. was measured.

(11) Thin wire workability evaluation In (8), the printed wiring board after forming a fine circuit pattern of L / S = 12/12 μm was evaluated by a thin wire appearance inspection and a continuity check with a laser microscope. The evaluation criteria are as follows.
◎: No problem in both shape and continuity ○: No short circuit or wire breakage, no problem ×: Short circuit, wire breakage

(12) Insulation reliability evaluation On the fine circuit pattern of L / S = 12/12 μm of the printed wiring board obtained in (8), a build-up material (BLA-3700GS manufactured by Sumitomo Bakelite Co., Ltd.) is used instead of the solder resist. A test sample was prepared by laminating and curing. Using this test sample, the continuous humidity insulation resistance was evaluated under the conditions of a temperature of 130 ° C., a humidity of 85%, and an applied voltage of 3.3 V. A resistance value of 10 ⁶ Ω or less was regarded as a failure. The evaluation criteria are as follows.
◎: No failure for 300 hours or more ○: Failure for 150 hours or more and less than 300 hours ×: Failure for less than 150 hours

(13) Warpage evaluation of semiconductor device Warpage of the semiconductor device obtained in (9) at normal temperature (23 ° C.) and 260 ° C. is measured using a temperature variable laser three-dimensional measuring machine (manufactured by Hitachi Technology and Service, model LS220-MT100MT50). Was used to evaluate. The semiconductor element surface was placed in the sample chamber of the measuring machine, the displacement in the height direction was measured, and the largest value of the displacement difference was taken as the amount of warpage. The evaluation criteria are as follows.
Normal temperature (23 ℃)
A: Warpage amount is less than 150 μm B: Warpage amount is 150 μm or more and less than 200 μm ×: Warpage amount is 200 μm or more and 260 ° C.
A: Warpage amount is less than 100 μm B: Warpage amount is 100 μm or more and less than 150 μm ×: Warpage amount is 150 μm or more

(14) Heat cycle test Four semiconductor devices obtained in (9) were treated under conditions of 60 ° C. and 60% for 40 hours, and then treated three times in an IR reflow furnace (peak temperature: 260 ° C.). And 500 cycles at −55 ° C. (15 minutes) and 125 ° C. (15 minutes). Next, using an ultrasonic imaging apparatus (manufactured by Hitachi Construction Machinery Finetech Co., Ltd., FS300), the semiconductor element and the solder bump were observed for abnormalities.
A: No abnormality in both semiconductor element and solder bump.
○: Cracks are seen in a part of the semiconductor element and / or solder bump, but there is no practical problem.
(Triangle | delta): A crack is seen in a part of semiconductor element and / or a solder bump, and there is a problem in practical use.
X: Both the semiconductor element and the solder bump are cracked and cannot be used.

(15) Glass transition temperature, storage elastic modulus at 250 ° C. The metal foil of the metal-clad laminate obtained in (7) was removed by etching, and a test piece of 6 mm × 25 mm was produced from the insulating layer from which the metal foil was removed. did. About this test piece, it heated up at 5 degree-C / min (frequency 1Hz) using DMA apparatus (The TA instrument company make, dynamic viscoelasticity measuring apparatus DMA983), and the storage elastic modulus E 'in 250 degreeC was each set. It was measured. The peak position of tan δ was defined as the glass transition temperature.

(Example 2)
A resin varnish was prepared in the same manner as in Example 1 except that the thickness of the first resin layer was 15 μm and the thickness of the second resin layer was 10 μm, and a prepreg, a metal-clad laminate, a printed wiring board, and a semiconductor device were produced. did.

(Example 3)
Using the following as the resin varnish (A) and the resin varnish (B), except that the thicknesses of the first resin layer and the second resin layer were changed to the values shown in Table 1, the same as in Example 1, A prepreg, a metal-clad laminate, a printed wiring board, and a semiconductor device were produced and evaluated.
17.5 parts by mass of 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (manufactured by Keisei Kasei Co., Ltd., BMI-80, double bond equivalent 285), naphthol-modified novolak epoxy resin (manufactured by Nippon Kayaku Co., Ltd.) NC-7000L, epoxy equivalent 230) 14.1 parts by mass, 3,3′-diethyl-4,4′-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd., Kayahard AA amine equivalent 63.5) 7.8 masses Part, 4,4′-butylidenebis (3-methyl-6-tert-butylphenol) (Ouchi Shinsei Chemical, Nocrack NS-30) 0.3 part by mass, epoxy silane coupling agent (Momentive Performance Materials) Made by A187) 0.2 parts by mass, silica particles (manufactured by Admatechs, SO-C2, average particle diameter 0.5 μm) 60.0 parts by mass in N Added methylpyrrolidone was adjusted to a nonvolatile content of 65% to prepare a resin varnish (A) was stirred using a high speed stirrer.
2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (manufactured by Keisei Kasei Co., Ltd., BMI-80, double bond equivalent 285) 30.2 parts by mass, naphthalenediol type epoxy resin (manufactured by DIC, HP -4032D, epoxy equivalent 150) 15.9 parts by mass, 3,3′-diethyl-4,4′-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd., Kayahard AA amine equivalent 63.5) 13.4 parts by mass, 4,4′-butylidenebis (3-methyl-6-tert-butylphenol) (Ouchi Shinsei Chemical, Nocrack NS-30) 0.3 parts by mass, epoxy silane coupling agent (Momentive Performance Materials, A187) 0.2 parts by mass, silica particles (manufactured by Admatechs, SO-C6, average particle size 2.2 μm) 40.0 parts by mass It was added to adjust to a non-volatile content of 65% Rupiroridon, to prepare a resin varnish (B) with stirring using a high speed stirrer.

Example 4
As the resin varnish (A), the following were used, and the prepreg and metal-clad laminate were the same as in Example 1 except that the thicknesses of the first resin layer and the second resin layer were changed to the values shown in Table 1. A board, a printed wiring board, and a semiconductor device were produced and evaluated.
2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (Kai Kasei Co., Ltd., BMI-80, double bond equivalent 285) 13.1 parts by mass, naphthol-modified novolak epoxy resin (Nippon Kayaku Co., Ltd.) NC-7000L, epoxy equivalent 230) 10.6 parts by mass, 3,3′-diethyl-4,4′-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd., Kayahard AA amine equivalent 63.5) 5.8 mass Part, 4,4′-butylidenebis (3-methyl-6-tert-butylphenol) (Ouchi Shinsei Chemical, Nocrack NS-30) 0.3 part by mass, epoxy silane coupling agent (Momentive Performance Materials) Manufactured by A187) 0.2 parts by mass, 70.0 parts by mass of silica particles (manufactured by Admatechs, SO-C1, average particle size 0.25 μm) - added methylpyrrolidone was adjusted to a nonvolatile content of 65% to prepare a resin varnish (A) was stirred using a high speed stirrer.

(Example 5)
As the resin varnish (B), the following were used, and the prepreg and the metal-clad laminate were the same as in Example 1 except that the thicknesses of the first resin layer and the second resin layer were changed to the values shown in Table 1. A board, a printed wiring board, and a semiconductor device were produced and evaluated.
2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (manufactured by Keisei Kasei Co., Ltd., BMI-80, double bond equivalent 285) 35.3 parts by mass, naphthalenediol type epoxy resin (manufactured by DIC, HP -4032D, epoxy equivalent 150) 18.6 parts by mass, 3,3′-diethyl-4,4′-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd., Kayahard AA amine equivalent 63.5) 15.7 parts by mass, 4,4′-butylidenebis (3-methyl-6-tert-butylphenol) (Ouchi Shinsei Chemical, Nocrack NS-30) 0.3 parts by mass, epoxy silane coupling agent (Momentive Performance Materials, A187) 0.2 parts by mass, silica particles (manufactured by Admatechs, SO-C5, average particle size 1.6 μm) 30.0 parts by mass It was added to adjust to a non-volatile content of 65% Rupiroridon, to prepare a resin varnish (B) with stirring using a high speed stirrer.

(Example 6)
As the resin varnish (A), the following were used, and the prepreg and metal-clad laminate were the same as in Example 1 except that the thicknesses of the first resin layer and the second resin layer were changed to the values shown in Table 1. A board, a printed wiring board, and a semiconductor device were produced and evaluated.
17.2 parts by mass of 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (manufactured by Keisei Kasei Co., Ltd., BMI-80, double bond equivalent 285), naphthol-modified novolak epoxy resin (manufactured by Nippon Kayaku Co., Ltd.) NC-7000L, epoxy equivalent 230) 13.8 parts by mass, 4,4′-diamino-3,3′-diethyl-5,5′-dimethyldiphenylmethane (manufactured by Ihara Chemical Co., Ltd., Cure Hard MED amine equivalent 70.5 ) 8.5 parts by mass, 0.3 parts by mass of 4,4′-butylidenebis (3-methyl-6-tert-butylphenol) (Nouchi NS-30 manufactured by Ouchi Shinsei Chemical), epoxysilane coupling agent (momentive performance)・ Materials, Inc., A187) 0.2 parts by mass, silica particles (manufactured by Admatechs, SO-C1, average particle size 0. 5 [mu] m) to 60.0 parts by weight of N- methylpyrrolidone was added was adjusted to a nonvolatile content of 65% and a resin varnish (A) was prepared by stirring using a high speed stirrer.

(Example 7)
As the resin varnish (A), the following were used, and the prepreg and metal-clad laminate were the same as in Example 1 except that the thicknesses of the first resin layer and the second resin layer were changed to the values shown in Table 1. A board, a printed wiring board, and a semiconductor device were produced and evaluated.
17.5 parts by mass of 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (manufactured by Keisei Kasei Co., Ltd., BMI-80, double bond equivalent 285), naphthol-modified novolak epoxy resin (manufactured by Nippon Kayaku Co., Ltd.) NC-7000L, epoxy equivalent 230) 14.1 parts by mass, 3,3′-diethyl-4,4′-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd., Kayahard AA amine equivalent 63.5) 7.8 masses Part, 2,6-di-tert-butyl-4-methylphenol (Ouchi Shinsei, NOCRACK 200) 0.3 parts by mass, epoxy silane coupling agent (Momentive Performance Materials, A187). 2 parts by mass, N-methylpyrrolidone was added to 60.0 parts by mass of silica particles (manufactured by Admatechs, SO-C1, average particle size 0.25 μm) Adjusted to volatile content of 65% to prepare a resin varnish (A) was stirred using a high speed stirrer.

(Example 8)
As the resin varnish (A), the following were used, and the prepreg and metal-clad laminate were the same as in Example 1 except that the thicknesses of the first resin layer and the second resin layer were changed to the values shown in Table 1. A board, a printed wiring board, and a semiconductor device were produced and evaluated.
16.1 parts by mass of 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (manufactured by Keisei Kasei Co., Ltd., BMI-80, double bond equivalent 285), biphenyl aralkyl epoxy resin (manufactured by Nippon Kayaku Co., Ltd., NC-3000H, epoxy equivalent 285) 16.1 parts by mass, 3,3′-diethyl-4,4′-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd., Kayahard AA amine equivalent 63.5) 7.2 parts by mass , 4,4′-butylidenebis (3-methyl-6-tert-butylphenol) (Ouchi Shinsei Chemical Co., Ltd., NOCRACK NS-30) 0.3 parts by mass, epoxy silane coupling agent (Momentive Performance Materials Co., Ltd.) Manufactured by A187) 0.2 parts by mass, silica particles (manufactured by Admatechs, SO-C1, average particle size 0.25 μm) 60.0 parts by mass in N Added methylpyrrolidone was adjusted to a nonvolatile content of 65% to prepare a resin varnish (A) was stirred using a high speed stirrer.

Example 9
As the resin varnish (A), the following were used, and the prepreg and metal-clad laminate were the same as in Example 1 except that the thicknesses of the first resin layer and the second resin layer were changed to the values shown in Table 1. A board, a printed wiring board, and a semiconductor device were produced and evaluated.
16.1 parts by mass of 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (manufactured by Keisei Kasei Co., Ltd., BMI-80, double bond equivalent 285), naphthylene ether type epoxy resin (manufactured by DIC, HP-6000, epoxy equivalent 285) 16.1 parts by mass, 3,3′-diethyl-4,4′-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd., Kayahard AA amine equivalent 63.5) 7.2 parts by mass , 4,4′-butylidenebis (3-methyl-6-tert-butylphenol) (Ouchi Shinsei Chemical Co., Ltd., NOCRACK NS-30) 0.3 parts by mass, epoxy silane coupling agent (Momentive Performance Materials Co., Ltd.) A187) 0.2 parts by mass, silica particles (manufactured by Admatechs, SO-C1, average particle size 0.25 μm) 60.0 parts by mass It was added to adjust to a non-volatile content of 65% Rupiroridon, to prepare a resin varnish (A) was stirred using a high speed stirrer.

(Example 10)
As the resin varnish (A), the following were used, and the prepreg and metal-clad laminate were the same as in Example 1 except that the thicknesses of the first resin layer and the second resin layer were changed to the values shown in Table 1. A board, a printed wiring board, and a semiconductor device were produced and evaluated.
19.0 parts by mass of 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (manufactured by Keisei Kasei Co., Ltd., BMI-80, double bond equivalent 285), anthracene type epoxy resin (YX-manufactured by Mitsubishi Chemical Corporation) 8800, epoxy equivalent 180) 12.0 parts by mass, 3,3′-diethyl-4,4′-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd., Kayahard AA amine equivalent 63.5) 8.5 parts by mass, 4 , 4'-butylidenebis (3-methyl-6-tert-butylphenol) (Ouchi Shinsei Chemical, Nocrack NS-30) 0.3 parts by mass, epoxy silane coupling agent (Momotivational Performance Materials, A187) ) 0.2 parts by mass, silica particles (manufactured by Admatechs, SO-C1, average particle size 0.25 μm) 60.0 parts by mass with N-methyl pyro Don was added was adjusted to a nonvolatile content of 65% to prepare a resin varnish (A) was stirred using a high speed stirrer.

(Example 11)
As the resin varnish (A), the following were used, and the prepreg and metal-clad laminate were the same as in Example 1 except that the thicknesses of the first resin layer and the second resin layer were changed to the values shown in Table 1. A board, a printed wiring board, and a semiconductor device were produced and evaluated.
15.1 parts by mass of bis- (3-ethyl-5-methyl-4-maleimidophenyl) methane (manufactured by Keisei Kasei Co., Ltd., BMI-70, double bond equivalent 221), naphthol-modified novolak epoxy resin (manufactured by Nippon Kayaku Co., Ltd.) NC-7000L, epoxy equivalent 230) 15.7 parts by mass, 3,3′-diethyl-4,4′-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd., Kayahard AA amine equivalent 63.5) 8.7 mass Part, 4,4′-butylidenebis (3-methyl-6-tert-butylphenol) (Ouchi Shinsei Chemical Co., Ltd., NOCRACK NS-30) 0.3 part by mass, epoxy silane coupling agent (Momentive Performance Materials) A187) 0.2 parts by mass, silica particles (manufactured by Admatechs, SO-C1, average particle diameter 0.25 μm) 60.0 parts by mass - added methylpyrrolidone was adjusted to a nonvolatile content of 65% to prepare a resin varnish (A) was stirred using a high speed stirrer.

(Example 12)
As the resin varnish (A), the following were used, and the prepreg and metal-clad laminate were the same as in Example 1 except that the thicknesses of the first resin layer and the second resin layer were changed to the values shown in Table 1. A board, a printed wiring board, and a semiconductor device were produced and evaluated.
13.4 parts by mass of 4,4′-diphenylmethane bismaleimide (manufactured by Keisei Kasei Co., Ltd., BMI-H, double bond equivalent 179), naphthol-modified novolac epoxy resin (manufactured by Nippon Kayaku Co., Ltd., NC-7000L, epoxy equivalent 230) 16.9 parts by mass, 3,3′-diethyl-4,4′-diaminodiphenylmethane (Nippon Kayaku Co., Ltd., Kayahard AA amine equivalent 63.5) 9.3 parts by mass, 4,4′-butylidenebis ( 3-methyl-6-tert-butylphenol) (Ouchi Shinsei Chemical Co., Ltd., NOCRACK NS-30) 0.3 parts by mass, epoxy silane coupling agent (Momentive Performance Materials Co., A187) 0.2 mass N-methylpyrrolidone was added to 60.0 parts by mass of silica particles (manufactured by Admatechs, SO-C1, average particle size of 0.25 μm). A resin varnish (A) was prepared by adjusting the non-volatile content to 65% and stirring using a high-speed stirring device.

(Example 13)
As the resin varnish (A), the following were used, and the prepreg and metal-clad laminate were the same as in Example 1 except that the thicknesses of the first resin layer and the second resin layer were changed to the values shown in Table 1. A board, a printed wiring board, and a semiconductor device were produced and evaluated.
13.2 parts by mass of polyphenylmethane maleimide (manufactured by Daiwa Kasei Co., Ltd., BMI-2300, double bond equivalent 179), 16.9 parts by mass of naphthol-modified novolak epoxy resin (manufactured by Nippon Kayaku Co., Ltd., NC-7000L, epoxy equivalent 230) Parts, 3,3′-diethyl-4,4′-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd., Kayahard AA amine equivalent 63.5), 9.3 parts by mass, 4,4′-butylidenebis (3-methyl- 6-tert-butylphenol) (Ouchi Shinsei Chemical Co., Ltd., NOCRACK NS-30) 0.3 parts by mass, epoxy silane coupling agent (Momentive Performance Materials, Inc., A187) 0.2 parts by mass, silica particles (Manufactured by Admatechs, SO-C1, average particle size 0.25 μm) N-methylpyrrolidone was added to 60.0 parts by mass to obtain a nonvolatile content 5% become so adjusted to prepare a resin varnish (A) was stirred using a high speed stirrer.

(Example 14)
As the resin varnish (A), the following were used, and the prepreg and metal-clad laminate were the same as in Example 1 except that the thicknesses of the first resin layer and the second resin layer were changed to the values shown in Table 1. A board, a printed wiring board, and a semiconductor device were produced and evaluated.
Phenol novolac type cyanate resin (Lonza, PT-60) 14.3 parts by mass, naphthol-modified novolac epoxy resin (Nippon Kayaku, NC-7000L, epoxy equivalent 230) 25.2 parts by mass, 2-phenyl- 4-methylimidazole (manufactured by Shikoku Kasei Co., Ltd., 2P4MZ) 0.3 parts by mass, epoxysilane coupling agent (manufactured by Momentive Performance Materials, A187) 0.2 parts by mass, silica particles (manufactured by Admatechs, SO -C1, average particle diameter 0.25 μm) N-methylpyrrolidone was added to 60.0 parts by mass to adjust the non-volatile content to 65%, and the mixture was stirred using a high-speed stirring device to prepare a resin varnish (A).

(Example 15)
As resin varnish (A) and resin varnish (B), the following were used, and the same procedures as in Example 1 were conducted except that the thicknesses of the first resin layer and the second resin layer were changed to the values shown in Table 1. A prepreg, a metal-clad laminate, a printed wiring board, and a semiconductor device were prepared and evaluated.
Phenol novolac type cyanate resin (Lonza, PT-60) 14.3 parts by mass, naphthol-modified novolac epoxy resin (Nippon Kayaku, NC-7000L, epoxy equivalent 230) 25.2 parts by mass, 2-phenyl- 4-methylimidazole (manufactured by Shikoku Kasei Co., Ltd., 2P4MZ) 0.3 parts by mass, epoxysilane coupling agent (manufactured by Momentive Performance Materials, A187) 0.2 parts by mass, silica particles (manufactured by Admatechs, SO -C1, average particle diameter 0.25 μm) N-methylpyrrolidone was added to 60.0 parts by mass to adjust the non-volatile content to 65%, and the mixture was stirred using a high-speed stirring device to prepare a resin varnish (A).
27.6 parts by mass of a phenol novolac-type cyanate resin (Lonza, PT-60), 31.9 parts by mass of a naphthalenediol type epoxy resin (manufactured by DIC, HP-4032D, epoxy equivalent 150), 2-phenyl-4- Methylimidazole (manufactured by Shikoku Kasei Co., Ltd., 2P4MZ) 0.3 parts by mass, epoxy silane coupling agent (manufactured by Momentive Performance Materials, A187) 0.2 parts by mass, silica particles (manufactured by Admatechs, SO-C5 The average particle size was 1.6 μm) N-methylpyrrolidone was added to 40.0 parts by mass to adjust the non-volatile content to 65%, and the mixture was stirred using a high-speed stirring device to prepare a resin varnish (B).

(Example 16)
As the resin varnish (A), the following were used, and the prepreg and metal-clad laminate were the same as in Example 1 except that the thicknesses of the first resin layer and the second resin layer were changed to the values shown in Table 1. A board, a printed wiring board, and a semiconductor device were produced and evaluated.
17.5 parts by mass of 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (manufactured by Keisei Kasei Co., Ltd., BMI-80, double bond equivalent 285), naphthol-modified novolak epoxy resin (manufactured by Nippon Kayaku Co., Ltd.) NC-7000L, epoxy equivalent 230) 14.1 parts by mass, 3,3′-diethyl-4,4′-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd., Kayahard AA amine equivalent 63.5) 7.8 parts by mass , 4,4′-butylidenebis (3-methyl-6-tert-butylphenol) (Ouchi Shinsei Chemical Co., Ltd., NOCRACK NS-30) 0.3 parts by mass, epoxy silane coupling agent (Momentive Performance Materials Co., Ltd.) Manufactured, A187) 0.2 parts by mass, alumina particles (manufactured by Admatechs, AO-802, average particle size 0.7 μm) 60.0 parts by mass Added N- methylpyrrolidone was adjusted to a nonvolatile content of 65% to prepare a resin varnish (A) was stirred using a high speed stirrer.

(Example 17)
As the resin varnish (B), the following were used, and the prepreg and the metal-clad laminate were the same as in Example 1 except that the thicknesses of the first resin layer and the second resin layer were changed to the values shown in Table 1. A board, a printed wiring board, and a semiconductor device were produced and evaluated.
26.4 parts by weight of 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (BMI-80, double bond equivalent 285 manufactured by Keisei Kasei Co., Ltd.), naphthol-modified novolak epoxy resin (manufactured by Nippon Kayaku Co., Ltd., NC-7000L, epoxy equivalent 230) 21.3 parts by mass, 3,3′-diethyl-4,4′-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd., Kayahard AA amine equivalent 63.5) 11.8 parts by mass 4,4'-butylidenebis (3-methyl-6-tert-butylphenol) (Nouchi NS-30 manufactured by Ouchi Shinsei Chemical Co., Ltd.), epoxy silane coupling agent (Momentive Performance Materials, A187) 0.2 mass parts, silica particles (manufactured by Admatechs, SO-C5, average particle diameter 1.6 μm) 40.0 mass parts N- Except that was adjusted to a nonvolatile content of 65% added methylpyrrolidone are a resin varnish was prepared in the same manner as in Example 1 to prepare a resin varnish (B) with stirring using a high speed stirrer.

(Comparative Example 1)
As the resin varnish (B), the following were used, and the prepreg and the metal-clad laminate were the same as in Example 1 except that the thicknesses of the first resin layer and the second resin layer were changed to the values shown in Table 1. A board, a printed wiring board, and a semiconductor device were produced and evaluated.
30.2 parts by mass of 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (BMI-80, double bond equivalent 285, manufactured by Keisei Kasei Co., Ltd.), naphthalenediol type epoxy resin (HP-4032D, manufactured by DIC) , Epoxy equivalent 150) 15.9 parts by mass, 3,3′-diethyl-4,4′-diaminodiphenylmethane (Nippon Kayaku Kayahard AA amine equivalent 63.5) 13.4 parts by mass, 4,4 ′ -Butylidenebis (3-methyl-6-tert-butylphenol) (manufactured by Ouchi Shinsei Chemical Co., Ltd., NOCRACK NS-30) 0.3 parts by mass, epoxy silane coupling agent (manufactured by Momentive Performance Materials, A187) 2 parts by mass, silica particles (manufactured by Admatechs, SO-C1, average particle diameter 0.25 μm) 40.0 parts by mass Except that was adjusted to a nonvolatile content of 65% added pyrrolidone is a resin varnish was prepared in the same manner as in Example 1 to prepare a resin varnish (B) with stirring using a high speed stirrer.

(Comparative Example 2)
As the resin varnish (B), the following were used, and the prepreg and the metal-clad laminate were made in the same manner as in Example 3 except that the thicknesses of the first resin layer and the second resin layer were changed to the values shown in Table 1. A board, a printed wiring board, and a semiconductor device were produced and evaluated.
2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (manufactured by Keisei Kasei Co., Ltd., BMI-80, double bond equivalent 285) 30.2 parts by mass, naphthalenediol type epoxy resin (manufactured by DIC, HP -4032D, epoxy equivalent 150) 15.9 parts by mass, 3,3′-diethyl-4,4′-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd., Kayahard AA amine equivalent 63.5) 13.4 parts by mass, 4,4′-butylidenebis (3-methyl-6-tert-butylphenol) (Ouchi Shinsei Chemical, Nocrack NS-30) 0.3 parts by mass, epoxy silane coupling agent (Momentive Performance Materials, A187) 0.2 parts by mass, silica particles (manufactured by Admatechs, SO-C2, average particle size 0.5 μm) 40.0 parts by mass It was added to adjust to a non-volatile content of 65% Rupiroridon, to prepare a resin varnish (B) with stirring using a high speed stirrer.

(Comparative Example 3)
A prepreg, a metal-clad laminate, a printed wiring board, and a semiconductor device were prepared and evaluated in the same manner as in Example 1 except that the second resin layer was not provided.

  The results are shown in Table 1.

5a carrier material 5b carrier material 11 fiber base material 100 resin substrate 101 fiber base material layer 103 resin layer 103a first resin layer 103b second resin layer 105 metal foil 60 vacuum laminating device 61 laminating roll 62 hot air drying device 200 metal-clad laminate DESCRIPTION OF SYMBOLS 300 Printed wiring board 301 Insulating layer 303 Metal layer 305 Insulating layer 307 Via hole 308 Electroless metal plating film 309 Electrolytic metal plating layer 311 Core layer 317 Build-up layer 400 Semiconductor device 401 Solder resist layer 407 Semiconductor element 410 Solder bump 413 Sealant

Claims (18)

A fiber substrate layer including a fiber substrate;
A resin layer that is provided on one or both sides of the fiber base layer and does not include the fiber base;
A resin substrate for forming a printed wiring board comprising:
The resin layer contains an epoxy resin and an inorganic filler,
The average particle diameter of the inorganic filler at the surface portion in the thickness direction of the resin layer, which is obtained from an observation image of a scanning electron microscope, is the average of the inorganic filler at the boundary between the resin layer and the fiber base layer. Resin substrate larger than particle size. The resin substrate according to claim 1,
The average particle size of the inorganic filler in the thickness direction surface portion of the resin layer is 0.04 μm or more and 5 μm or less,
The resin substrate whose average particle diameter of the said inorganic filler in the boundary part with the said fiber base material layer of the said resin layer is 0.04 micrometer or more and less than 5 micrometers. In the resin substrate according to claim 1 or 2,
The content of the inorganic filler at the boundary between the resin layer and the fiber base layer is FC ₁ ;
When the content of the inorganic filler in the thickness direction surface of the resin layer was FC _2,
The resin layer is a resin substrate that satisfies a relationship of FC ₁ > FC ₂ . In the resin substrate according to claim 3,
The content of the inorganic filler (FC ₁ ) at the boundary portion between the resin layer and the fiber base layer is 50% by mass or more and 90% by mass or less,
The content of the inorganic filler in the thickness direction surface portion (FC ₂₎ is 60 mass% or less than 20 wt%, the resin substrate of the resin layer. In the resin substrate according to claim 4,
The resin layer is
A first resin layer in contact with the fiber base layer;
A second resin layer provided on the side opposite to the fiber base layer of the first resin layer, and constituting the thickness direction surface portion of the resin substrate;
Including
The first resin layer is composed of an epoxy resin composition (A),
Said 2nd resin layer is a resin substrate which consists of an epoxy resin composition (B) of a kind different from an epoxy resin composition (A). In the resin substrate according to claim 5,
A resin substrate that does not include a clear layer interface in the resin layer. In the resin substrate according to claim 5 or 6,
The thickness of the first resin layer is 5 μm or more and 100 μm or less,
A resin substrate, wherein the second resin layer has a thickness of 0.5 μm or more and 25 μm or less. In the resin substrate as described in any one of Claims 5 thru | or 7,
The epoxy resin constituting the epoxy resin composition (A) is bisphenol type epoxy resin, novolac type epoxy resin, biphenyl type epoxy resin, aralkyl type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, and dicyclopentadiene type epoxy. A resin substrate that is one or more selected from the group consisting of resins. The resin substrate according to any one of claims 5 to 8,
A resin substrate in which the inorganic filler constituting the epoxy resin composition (A) is one or more selected from the group consisting of talc, alumina, glass, silica, mica, aluminum hydroxide, and magnesium hydroxide. In the resin substrate as described in any one of Claims 5 thru | or 9,
The epoxy resin constituting the epoxy resin composition (B) is bisphenol type epoxy resin, novolac type epoxy resin, biphenyl type epoxy resin, aralkyl type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, and dicyclopentadiene type epoxy. A resin substrate that is one or more selected from the group consisting of resins. In the resin substrate as described in any one of Claims 5 thru | or 10,
A resin substrate in which the inorganic filler constituting the epoxy resin composition (B) is one or more selected from the group consisting of talc, alumina, glass, silica, mica, aluminum hydroxide, and magnesium hydroxide. In the resin substrate as described in any one of Claims 1 thru | or 11,
The resin layer further includes a bismaleimide compound,
The bismaleimide compound is 4,4′-diphenylmethane bismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, bis- (3-ethyl-5-methyl-4-maleimidophenyl) methane. And a resin substrate that is one or more selected from the group consisting of polyphenylmethanemaleimide. The resin substrate according to any one of claims 1 to 12,
The resin substrate further includes a cyanate resin. In the resin substrate as described in any one of Claims 1 thru | or 13,
The fiber substrate is a glass fiber substrate composed of one or more selected from E glass, S glass, D glass, T glass, NE glass, UT glass, L glass, HP glass and quartz glass, Resin substrate. In the resin substrate as described in any one of Claims 1 thru | or 14,
The resin substrate whose thickness of the said resin substrate is 10 micrometers or more and 500 micrometers or less.   A metal-clad laminate in which a metal foil is provided on one or both sides of the resin substrate according to any one of claims 1 to 15 or a laminate obtained by superimposing two or more of the resin substrates.   The printed wiring board by which the circuit layer is provided in the single side | surface or both surfaces of the resin substrate as described in any one of Claims 1 thru | or 15.   The semiconductor device which mounted the semiconductor element on the said circuit layer of the printed wiring board of Claim 17.

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